SYNTHESIS OF TIMOSAPONIN BII

Field of the Invention

The present invention relates to synthesis of timosaponin BII and related compounds.

Background of the Invention

Timosaponin BII, also called prototimosaponin AHI, (25S)-26-0-β-D-glucopyranosyl-22- hydroxy-5β-furostane-3 β,26-diol-3-O-β-D-glucopyτanosyl-(l -→2)-β-D-galactopyranoside, having the formula:

has been reported as having useful pharmaceutical properties, including activities against dementia and stroke, and abilities to lower blood sugar levels, inhibit platelet aggregation and clear free radicals. See WO-A-99/16786 (EP-A-1024146), WO-A-2005/105108 and WO-A-2005/105824 and the publications referred to therein, the disclosures of all of which are incorporated herein by reference.

Hitherto, the active agent has been extracted from plant sources, particularly the rhizomes of Ammairhena asphodeloides Bge. The relatively small amounts of the compound available in this way limits the potential commercial development of the compound and

its physiologically active analogues and derivatives.

The present invention is based on our surprising finding of a synthetic route from the more readily available material sarsasapogenin, providing timosaponiπ BII in good yield with an economically acceptable number of reaction steps and without the need for excessive intermediate separation or purification steps.

The sarsasapogenin is available with an acceptable purity via known processes, for example as described in WO-A-2004/037845 and WO-A-2006/048665, the disclosures of which are incorporated herein by reference.

The finding of a new synthetic route to timosaponin BII, according to the present invention, opens up the possibilities to develop novel physiologically active analogues and derivatives of timosaponin BII. The present invention thus extends also to such novel analogues and derivatives.

Brief Description of the Invention

In a first aspect, the present invention provides a method of preparing a compound of general formula I:

wherein, independently of each other, R] represents hydrogen or an ester, ether or sugar residue; R ₂ represents hydrogen; and R3 represents hydrogen or a sugar residue; or a protected form thereof in which any one or more of the groups R ₁ and R ₃ are, independently from each other, protected by a removable protecting group to prevent an undesirable reaction of the group;

which comprises selectively reducing a diketone compound of general formula II:

wherein, independently of each other, Ri represents hydrogen or an ester, ether or sugar residue; and R ₃ represents hydrogen or a sugar residue; or a protected form thereof in which any one or both of the groups R _t and R] are, independently from each other, protected by a removable protecting group to prevent an undesirable reaction of the residue;

using a borohydride reducing agent in a suitable solvent.

The expression "protected" used herein in the context of any residue will, unless the context otherwise requires, be taken to refer to the use of a removable protecting group to

prevent an undesirable reaction of the residue. The expression "protecting group" and like expressions will be understood correspondingly.

Where the stereochemistry of a bond or carbon centre is defined, this is shown using the solid-wedge-boαd and dotted-wedge-bond convention, a solid wedge representing a bond up (β) from the plane of die paper and a dotted wedge respresenting a bond down (α) from the plane of the paper. Bonds that are stereochemically undefined are shown using an unwedged bond ( — ) or a wavy line bond (~). Bonds within the steroidal fused ring system are shown stereochemically undefined and any definition of their stereochemistry or stereochemistry options is to be understood from knowledge of the molecules under consideration.

The following abbreviations for sugars are used herein: Gal (galactose), GIc (glucose), Rha (rhamnose), Fuc (fucose), XyI (xylose), Ara (arabinose).

Preferred starting materials for the method defined above are compounds of general formula Ha:

wherein, independently of each other,

Ri represents hydrogen or an ester, ether or sugar residue; and

Rj represents hydrogen or a sugar residue; or a protected form thereof in which any one or both of the groups R ₍ and R3 are,

independently from each other, protected by a removable protecting group to prevent an undesirable reaction of the residue.

Most preferred starting materials for the method defined above are compounds of general formula Hb:

wherein, independently of each other,

R ₁ represents hydrogen or an ester, ether or sugar residue; and

R ₃ represents hydrogen or a sugar residue; or a protected form thereof in which any one or both of the groups Ri and R3 are, independently from each other, protected by a removable protecting group to prevent an undesirable reaction of the residue.

Il is especially preferred that lbe method is used in the preparation of timosaponin BII or a prodrug form thereof.

Protecting groups, if present, may if desired be simultaneously or subsequently removed in conventional manner. The use and removal of appropriate protecting groups will be well within the capacity of those skilled in this art.

The diketone function of the compound of general formula π bas been found to be substantially inert to reaction with esterifying, etherifying and glycosylating agents for adjusting the residues R| and R ₃ . The diketone compound of formula II thus provides a suitable intermediate species for coupling reactions for adding optionally protected ester, ether and/or sugar moieties to develop the residues R) and R ₃ .

The compound of general formula I wherein R ₁ represents hydrogen or an ester, ether or sugar residue, R ₂ represents hydrogen and R ₃ represents hydrogen or a sugar residue, or a protected form thereof, prepared as defined above, may if desired be subjected to a reaction to introduce an ester or ether residue in place of the hydrogen for R ₂ . Such reactions Io convert an OH residue to an O-ester or O-ether residue arc well known to those skilled in this art. In some cases it may be desirable to use an activated form of the compound of general formula I, for example a form of the compound in which the OH group OR ₂ is converted to an 0-A ⁺ salt, wherein A ⁺ is a cation, e.g. sodium. In some cases it may be desirable to use an activated form of a reagent for introducing an ester or ether residue, for example a halide form to assist a substitution reaction to introduce the residue. The selection of such features is well known to those skilled in this art.

The method of the invention can be performed on any scale from laboratory through pilot plant to commercial (kilogram) scale preparing quantities of product in excess of lkg per batch.

The above method makes available compounds of general formula I and protected forms thereof which are per se novel compounds, and they therefore constitute a further aspect of the present invention. In accordance with a second aspect of the present invention, therefore, there are provided compounds of general formula I:

wherein, independently of each other,

R ₁ denotes H, COCH ₃ , CO(CH ₂ ) _n CH ₃ (n = 1-6), C _m H _2ra+ i (m = 1-6), Gal, GIc, β-D-Glc-(l-→2)-β-D-Ga], β-D-Glc-(l→4)-β-D-Gal, β-D-Glc-(l→2)-β-D-Glc, β-D-Glc-(l→4)-β-D-Glc, β-D-Glc-(l→6)-β-D-Glc, α-L-Rha-(l→2)-β-D-Glc, α-L-Rha-(l→4)-β-D-Glc, α-L-Rha-(l→6)-β-D-Gal, α-L-Rlia-(l→4)-[α-L-Rha-(l→2)]-β-D-Glc, β-D-Glc-(l→4)-[α-L-Rlia-(l-→2)]-β-D-Glc, β-D-Glc-( 1 →2)-[α-L-Rha-(l →4)]-β-D-Glc, β-D-Glc-( 1 ->4)-[α-L-Rlia-( 1 →2)] -β-D-Gal, α-L-Rha-(l->4)-[β-DGlc-(l→2)]-β-D-Glc, β-D-Glc-(l→4)-β-D-Glc-(l-→4)-β-D-Gal, β-D-Glc-(l→4)-β-D-Glc-(l→2)-β-D-Gal, β-D-Glc-(l→4)-β-D-Glc-(l→4)-β-D-Glc or β-D-Glc-(l->4)-β-D-Glc-(l-→2)-β-D-Glc;

R ₂ denotes H or C^ _m +i (m = 1-6); and

R ₃ denotes H, α-L-Fuc, β-D-Xyl, β-D-Ara, α-L-Rha, β-D-Gal and β-D-Glc;

excluding the compounds disclosed in WO-A-99/16786, WO-A-2005/105108 and

WO-A-2005/105824 and the publications referred to therein.

In one particular embodiment of the second aspect of the present invention, the compounds are prepared using the method of the first aspect of the invention.

The intermediate compounds of general formula II, used in the method of the present invention, are also per se novel compounds, and they therefore constitute a further aspect

of the present invention.

In accordance with a third aspect of the present invention, therefore, there are provided compounds of general formula II:

wherein, independently of each other, R] represents hydrogen or an ester, ether or sugar residue; and R ₃ represents hydrogen or a sugar residue; or a protected form lhereof in which any one or both of the groups R| and R ₃ are, independently from each other, protected by a removable protecting group,

Preferred compounds are those of general formulae IIa and lib as defined above.

Most preferred compounds are those of general formula lib wherein, independently of each other,

Ri denotes H, COCH ₃ , CO(CH ₂ ) _n CH ₃ (n = 1-6), C ₁₇₁ H _3n ,,, (m ^» 1-6), Gal, GIc, P-D-GIc-(I →2)-β-D-Gal, β-D-Glc-(l -→4)-β-D-Gal, β-D-Glc-(l →2)-β-D-Glc, β-D-GIc-(l→4)-β-D-Glc, β-D-Glc-(l-→6)-β-D-Glc, α-L-Rha-(l →2)-β-D-Glc, α-L-Rha-(l-→4)-β-D-Glc, α-L-Rha-(l→6)-β-D-Gal, α-L-Rha-(l→4)-[α-L-Rha-(l →2)]-β-D-Glc, β-D-Glc-(l-→4)-[α-L-Rha-(l-→2)]-β-D-Glc, β-D-Glc-(l -»2)-[α-L-Rha-(l -→4)]-β-D-Glc, β-D-Glc-(l→4)-[α-L-Rha-(l→2)]-β-D-Gal,

α-L-Rha-(l→4)-[β-D ^Q lc-(l→2)]-β-D-Glc, β-D-Glc-(l-→4)-P-D-Glc-(l-→4)-β-D-σal, β-D-Glc-{l-→4)-β-D-Glc-(l→2)-β-D-Gal, β-D-Glc-(l→4)-β-D-Glc-(l→4)-β-D-Glc or β-D-Glc-Q -→4)-β-D-Glc-(l→2)-β-D-Glc; and

R ₃ denotes H, α-L-Fuc, β-D-Xyl, β-D-Ara, α-L-Rha, β-D-Gal and β-D-Glc.

Detailed Description of the Invention

Selective Reduction of (he Diketone of General Formula II

The preferred reducing agent is an unhindered borohydride reducing agent. The expression "unhindered" used herein refers to an absence of organic substituents of the borohydride species.

A suitable borohydride reducing agent is sodium borohydride.

The solvent for the selective reduction of the diketome of general formula II is selected according to the particular reducing agent used. The solvent is preferably a mixture of a polar organic solvent, such as, for example, an alkyl alcohol having more than one carbon atom, and a non-polar organic solvent which is miscible with the polar solvent, such as, for example, a haloalkane, e.g. dichloromethane. The relative proportions of the polar and non-polar solvents can be selected by a person skilled in the art according to the other compounds to be used. The polar solvent may conveniently be present in a volume excess, for example in a ratio polar:non-polar in the range of about 2:1 to about 20:1, for example about 4: 1 to about 10: 1 by volume. The solvent is preferably non-aqueous.

Protecting groups for R _| and R ₃ in the diketone of general formula II may be selected from conventional protecting groups according to the reaction conditions and the nature of the residue to be protected. For details of protecting groups that may be used, and the removal reactions for them, see T. W. Green, P. G M. Wuts, "Protective Groups in

Organic Synthesis", 4 ^Ul Edition, Wiley-Interscience, New York, 2006. In particular, different protecting groups can be used to protect different parts of one or more of the molecules involved in the reaction, particularly different OH groups of the molecule(s), and the protecting groups can be selectively removed as desired.

By way of example, suitable protecting groups for OH groυp(s) of sugar moieties of the diketone of general formula II may be selected from acetyl (Ac), pivaloyl (Piv) and benzoyl (Bz) groups. Suitable protecting groups for other OH group(s) of the diketone of general formula II may be selected from silyl ether protecting groups, for example t.butyldimethylsilyl (TBS), t.butyldiphenylsilyl (TBDPS), trimethylsilyl (TMS), triethylsilyl (TES) and triisopropylsϋyl (TIPS). Ester and ether residues in the diketone of general formula II may not need to be protected, but if particular active substituents of the residues are present, suitable protecting groups can be selected by the person skilled in this art.

Removal of the protecting groups can be achieved in conventional manner according to the nature of the protecting group. For example, treatment of a compound including an acetylated or benzoylated sugar moiety with NaOMe in methanol at around pH 10 with stirring, for a period of time, generally 3-6 hours, at room temperature results in the complete de-O-acetylation or de-O-benzoylation. The reaction solution can then be neutralized with Amberlite IR 120 (H ⁺ ) resin. The organic phase can then be concentrated to dryness and the residue purified on column chromatography to afford the desired deacylated material. Those skilled in the art would recognize that other standard procedures are available for the same material, such as treatment with ammonia in methanol.

Coupling Reactions Performed on a Suear or on a Dikelone of General Formula II

Sugar-to-sugar coupling reactions may be used to prepare di-, tri- or higher saccharide

sugars for coupling. A sugar molecule may be coupled to any OH group of a diketone of general formula II. Such an OH group may be a sugar OH group or a non-sugar OH group.

For these reactions, some OH groups of the reacting molecules may be protected so that the coupling is appropriately directed. Ester and ether protecting reactions performed on an OH residue of a sugar are standard organic synthesis reactions which will be familiar to those skilled in the art and require no further discussion here.

Sugar coupling reactions generally fall into two categories, according to how the sugar moiety to be coupled is activated. One general category of reaction uses a thioglycoside (e.g. thioethyl sugar or thio-2-propyl sugar) as the activated sugar moiety for coupling, in the presence of a suitable catalyst such as a catalytic amount of N-iodosuccimide (NIS) and an iodine, silyl or silver cocatalyst. The second general category of reaction uses a sugar trihaloacetimidate (e.g. trichloroacetimidate) as the activated sugar moiety for coupling. The activated sugar is coupled, via the activated carbon centre, to a glycoside acceptor, namely another sugar molecule (via an unprotected OH group thereof) or a diketone of general formula II (via an unprotected OH group thereof, including an unprotected OH group of a sugar moiety of the diketone).

The first category coupling reaction typically proceeds as follows: To a solution of thioglycoside and the glycoside acceptor in an anhydrous solvent (such as toluene, dichloromelhaπe or ether), is added a catalytic amount of N-iodosuccimide (NIS) and trimetliylsilyl lrifluorosulfonate (TMSOTf). The mixture is stirred at -2O ⁰ C to room temperature for a period of time, generally 0,5-2 hours, and then adjusted to pH 7.0 with triethylamine. Concentration and column purification then affords the desired compound. Those skilled in the art will readily be able to identify several alternative options for this reaction of the same material, such as using NIS-I2 or NIS-AgOTf or NIS-TfOH as catalyst.

The second category coupling raction typically proceeds as follows: To a solution of sugar trichloroacetimidat ^β and the glycoside acceptor in an anhydrous solvent (such as toluene, dichloromethane or an ether) is added a catalytic amount of a suitable catalyst such as trimethylsilyl trifluorosulfonate (TMSOTf), BF ₃ ^Et ₂ O, or HClO ₄ -SiO ₂ . The mixture is stirred at -2O ⁰ C to room temperature for a period of time, generally 0.5-2 hours, and then adjusted to pH7.0 with triethylamine. Concentration and column purification afforded desired compound.

In the present invention, such coupling reactions may be used to couple a sugar molecule to another sugar molecule, which may be the same or a different sugar, to assemble larger sugar molecules, or to a compound of general formula I or II (including Ua and lib) in which one or both of ORi and OR ₃ represents OH.

For example, such coupling reactions may be used to couple a sugar molecule to another sugar molecule, which may be the same or a different sugar, to assemble larger sugar molecules, or to a compound of general formula II (including IIa and Ob) in which one or both of Ri and R ₃ represents hydrogen.

The stereochemistry of the coupling reaction is controllable, according to the portions of the sugar molecule in the vicinity of the activated Cl carbon atom of the sugar molecule. If the activated Cl carbon atom is adjacent to a C2 carbon atom which carries an O-acyl group (-0-C(O)- linkage), then the resulting bond between the Cl carbon atom of the sugar molecule and the glycoside acceptor is controlled usually to be equatorial (β) to the plane of the sugar ring. This result is found, irrespective of which category of coupling reaction is used, irrespective of whether the activating group at C 1 is α or β to the plane of the sugar ring, and irrespective of whether the glycoside acceptor is another sugar molecule or a compound of general formula II in which one or both of Ri and R ₃ represents hydrogen. It is believed that this effect is caused by the coupling reaction

progressing through a cyclic intermediate involving the axial (α) -0-C(O)- linkage carried by the C2 carbon atom of the sugar and the activating group at the Cl carbon atom, the cyclic intermediate being configured in such a way that coupling of the sugar to the glycoside acceptor is always such that the coupling bond is equatorial (β) to the plane of the sugar ring.

It is possible in principle for a di- or higher polysaccharide to be assembled separately from the steroid molecule, and then coupled to a steroid molecule of general formula I in which 0R| is OH. We have found, however, that there is often a substantial reduction in the yield of the preferred 3β-saponin when a pre-assembled di- or higher polysaccharide is coupled directly to a 3β-OH steroidal aglycone of this type. It appears that a mixture of 3α- and 3β-saponins is typically produced, which can be impossible to separate. Therefore, it is preferred to assemble complex sugars for the desired end product of general formula I in situ on the compound of formula II, prior to converting the compound of formula II to the compound of formula I.

Coupling of a sugar moiety to a sugar moiety, whether in situ on the steroid molecule or separately from it, and coupling of a sugar moiety to a non-sugar OH group of the steroid molecule, for example the compound of formula II, can be achieved using either category of coupling.

Ester Residues in the Compounds of General Formulae I and II

Ester residues in the compounds of general formulae I and II, including such residues introduced in place of H for R ₂ as described above, may be any ester formable by reaction of an OH group with an ester-forming acid or activated derivative thereof. The organic acid may, for example, be an aliphatic carboxylic acid or amino acid. Without limitation, the organic ester group may, for example, be selected from: cathylate (ethoxycarbonyloxy), acetate, succinate, propionate, n-butyrate, i-butyrate, valerate,

isovalerate, n-caproate, iso-caproate, diethylacctate, octanoate, decanoate, laurate, myristate, palm ^j tate, stearate, benzoate, phenylacetate, phenylpropionate, cinnamate, phthalyl, glycinate, alaninate, validate, phenylalaninate, isoleucinate, methioninate, argininate, aspartate, cysteinate, glutarainalc, histidinate, lysinate, prolinate, serinate, threoninate, tryptophanate, tyrosiπate, ftαmerate, maleate, substituted aliphatic, e.g. chloroacetate, methoxyacetate, protected amino acid ester groups, e. g. Boc- aminoglycinate (Boc=t-butoxycarbonyl), Boc-aminovalinate, CBZ-aminoglycinate (CBZ=benzyloxycarbonyl), CBZ-aminoalinate, and substituted aromatic ester groups, e. g. p-bromobenzoyloxy, m-bromobenzoyloxy, p-methoxybenzoyloxy, clilorobenzoate such as p-chlorobenzoyloxy, dichlorobenzoate such as 2,4-dichlorobenzoyloxy, πitrobenzoate such as p-nitrobenzoyloxy or 3, 5-dinitrobenzoyloxy, etc,

Ether Residues in the Compounds of General Formulae I and II

Ether residues in the compounds of general formulae I and II, may be any ether formable by reaction of an OH group of the compound of general formulae I or II, or an OH-activated form thereof, with an ether-forming compound such as an aliphatic, olefinic or cycloaliphatic hydrocarbon bearing a suitable leaving group to couple via a substitution reaction with the OH group or activated derivative thereof. The hydrocarbon may, for example, be a straight or branched alkane, alkene, alkyne, cycloalkane or cycloalkene, suitably containing up to about 15 carbon atoms, for example between 1 and about 10 carbon atoms, e.g. 1 to 6 carbon atoms. The suitable leaving group may, for example, be a halo atom such as chloro or bromo, or an organic sulfonyl leaving groups such as tosyl.

Sugar Residues in the Compounds of General Formulae I and II

Examples of sugar residues for Ri and Rj include mono-, di- and tri-saccharides and higher polysaccharides and acylated forms thereof. Without limitation, such a sugar may, for example, be a mono aldose or ketose having 5 or 6 carbon atoms, preferably in the

cyclised furanose or pyranose form, either as α or β anomer and having D or L optical isomerism. Examples of suitable sugars include glucose, mannose, fructose, galactose, maltose, cellobiose, sucrose, rhamnose, xyulose, arabinose, fucose, quinovose, apiose, lactose, galactose-glucose, glucose-arabinose, fucose-glucose, rhamnose-glucose, rbamnose-galactose, glucose-glucose-glucose, glucose-glucose-galactose, gluctose-rhamnose, mannose-glucose, rhamnose-(glucose)-glucose, rhamnose-(rhamnose)-glucose, glucose-(rhamnose)-glucose, glucose-(rhamnose)-galaclose, giucose-(rhamnose)-rhamnose, galactose-(rhamnose)-galactose, and acylated (e.g. acetylated) derivatives thereof.

Compositions

The compounds of general formula I, for example timosapoπin BII, prepared using the method of the present invention, may be included in pharmaceutical compositions as described in the prior art and other conventional pharmaceutical forms.

Preparation of the Compounds of General Formula II

The compounds of general formula Il in which R| and R ₃ are not sugar residues, and their protected forms, used as starting materials in the above method, can be prepared from the corresponding F-ring-closed spirostane steroidal sapogenin by an oxidative F-ring opening reaction. Such a reaction may, for example, be carried out by mixing a

3-OH-protecled form of the sapogenin and NaPICO ₃ in an aqueous organic solvent such as CH ₂ Cl ₂ -acetone-1.0 mM aqueous Na ₂ EDTA and adding (e.g. dropwise) an aqueous solution of oxone (2KHSO _S -KHSO ₄ -K ₂ SO ₄ ).

The reaction initially provides an equilibrium mixture of the unreacted 3-0-protected sapogenin and a correspondingly 3-0-protected compound of general formula II in which OR ₃ = OH. Coupling of a sugar residue in place of R ₃ then drives the equilibrium

towards the ring-opened form (general formula II).

The sapogenin starting material is selected from sarsasapogenin, episarsasapogeniα, smilagenin and epismilagenin, according to the desired stereochemistry permutations at the two chiral centres denoted by wavy lines in general formula I. To provide the permutation of stereochemistry required for timpsaponin BII (see the formula on page 1), sarsasapogenin is used.

Examples

The following Examples are provided for further illustration of the present invention, and without in any way limiting the protection as defined by the appended claims and the foregoing description.

In the Examples, percentages and proportions of solid materials are by weight unless otherwise stated or unless the context otherwise requires. Percentages and proportions of liquid materials are by volume unless unless otherwise stated or unless the context otherwise requires. Percentages and proportions of solid materials in liquids are by weight solid to volume of liquid unless unless otherwise stated or unless the context otherwise requires. Abbreviations: NIS = N-iodosuccimide; TMSOTf = ^• Me ₃ SiOTf = trimethylsilyl trifluorasulfonate; anhyd. = anhydrous; DMF = dimetbylformamide; TEA = triethylamine; Me = methyl; Et = ethyl; Bu = butyl; Pr = propyl. Optical rotations were determined at 25 ⁰ C with a Perkin-Elmer Model 241-Mc automatic polarimeter. ¹ H NMR and ¹³ C NMR were recorded with a Briiker ARX 400 spectrometer for solutions in CDCl ₃ or D ₂ O or CD ₅ N. Chemical shifts are given in ppm downfield from internal Me ₄ Si. Mass spectra were measured using a MALDI TOF-MS with α-cyano-4-hydroxycinnamic acid (CCA) as matrix. Thin-layer chromatography (TLC) was performed on silica gel HF254 with detection by charring with 30% (v/v) H ₂ SO^ in MeOH or in some cases by UV detector. Column chromatography was conducted by elution of a column of silica gel

(100 - 200 mesh) with EtO Ac-petroleum ether (60 - 90 ⁰ C) as the eluent. Solutions were concentrated at < 60 ⁰ C under reduced pressure.

Examplel The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane- 3β,26-diol-3-0-β-D-glucopyranosyl-(l-»2)-β-D-galactopyra noside (14)

The overall reaction scheme is as follows:

Patent-scheme 1 Preparation of (2)

Compound 1 (sarsasapogenin; 13.0 g, 31.2 ramol) was dissolved in DMF (100 mL), and TBSCl (6.0 g, 39.8 mmol) was added to the solution. The mixture was stirred at 7O ⁰ C

- 90 ⁰ C for 8 h, at the end of which time TLC (petroleum ether-EtOAc, 30:1) indicated that all starting materials were consumed. The reaction mixture was diluted with petroleum ether (300 mL). This organic phase was washed with water (450 mL X 2) and dried over anhydrous Na ₂ SO ₄ , the solid was then filtered off, and the filtrate was concentrated under vacuum to give a white solid 2 (16.1 g, 97%): ¹ H NMR (400 MHz,

CDCl ₃ ): (54.37-4.42 (m, 1 H, H-16), 4.01 (br s, 1 H, H-3), 3.95 (dd, 1 H, J 2.6, 10.9 Hz ₁

H-2δa), 3.29 (d, 1 H, J 11.8 Hz, H-26b), 1,07 (d, 3 H, /7.1 Hz, 21 -CH ₃ ), 0.98 (d, 3 H, J

6.7 Hz, 27-CH,), 0.94 (s, 3 H, 19-CHj), 0.87 (s, 9 η, t-Bu), 0.75 (s, 3 η, 18-CH,), 0.001

(s, 6 η, 2 CH ₃ ). ¹³ C NMR (100 MHz, CDCl ₃ ): δ 109.6, 81.0, 67.3, 65.0, 62.1, 56.5, 42.1, 40.6, 40.0, 36.4, 35.3, 35.1, 27.0, 26.8, 26.7, 25.8, 25.7, 23.9, 20.9, 18.0, 16.4, 16.0, 14.3.

Preparation of (3) and (4)

To a mixture of compound 2 (16.1 g, 30 mmol) and NaHCO ₃ (49 g, 0.58 mmol) in

CHjCl ₂ -acetone-l .0 mM aqueous Na ₂ EDTA (450 mL, 1 :1 :1, v/v/v) was added dropwise a solution of Oxone (2KHSO _J -KHSO ₄ -K ₂ SO ₄ ) (105 g, 0.169 mol) in 25 mL of 1.0 mM aqueous Na ₂ EDTA. The mixture was stirred at room temperature overnight. TLC

(petroleum ether-EtOAc, 10:1) indicated that all starting materials were consumed. The mixture was concentrated, then diluted with CH ₂ Cl ₂ . The organic phase was washed with water, dried over anhydrous Na ₂ SO ₄ , concentrated, and purified by column chromatography (petroleum ether-EtOAc, 20: 1), to afford 3 and 4 as a mixture of white solid (13.5 g, 81%).

Preparation of (6)

To a mixture of compounds 3 and 4 (2.25 g, 4.1 mmol) and 5 (3.56 g, 4.8 mmol, commercially available) in anhyd CH ₂ Cl ₂ (36 mL) was added Me ₃ SiOTf (86 μL, 0.47 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for

40 min, at the end of which time TLC (petroleum ether-EtOAc, 4: 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with triethylamine (TEA), then concentrated. Column chromatography (petroleum etlier-EtOAc, 6: 1) of the residue gave 6 as a foamy solid (3.7 g, 80%): ¹ H NMR (400 MHz, CDCl ₃ ): 58.02-7.27 (m, 20 H, 4 PhCO), 5.90 (I, 1 H, 79.6 Hz, H-3 ^Glc ), 5.67 (t, 1 H, 79.7 Hz, H-4 ^σfc ), 5.53 (dd, 1 H, /7.8, 9.8 Hz, H-2 ^clc ), 4.86 (d, 1 H.77.8 Hz ₁ H-l ^Glc ), 4.63 (dd, 1 H, 73.3, 12.1 Hz, H-6a ^σfc ), 4.51 (dd, 1 H, /5.3, 12.1 Hz, H-6b ^αic ), 4.19-4.14 (m, 1 H, H-5 ^G|C ), 4.05 (br.s, 1 H, H-3 ⁸ "), 3.87 (dd, 1 H ₁ 75.3, 9.4 Hz, H-26a ^Sl "), 3.31 (dd, 1 H ₁ 7 7.3, 9.4 Hz, H-26b ^So1 ), 0.95 (s,3 H, 19-CH ₃ ), 0.89 (d, 3 H, 76.6 Hz, 21-CR,), 0.88 (s, 9 H ₁ t-Bu ofTBS), 0.79 (d, 3 H, 76.6 Hz, 27-CHj), 0.72 (s, 3 H, 18-C ¹ H,), 0.01 (s, 6 H, 2 CHj). ¹³ C NMR (400 MHz, CDCl ₃ ): £ 218.4, 213.6, 166.1, 165.8, 165.2, 165.1, 133.3, 133.1 , 133.1, 133.0, 129.7, 129.7, 129.5, 129.3, 128.8, 128.7, 128.3, 128.3, 128.5, 101.4, 75.3, 72.9, 72.0, 71.9, 69.8, 67.2, 66.4, 63.2, 51.2, 43.2, 42.0, 39.8, 39.5, 39.1, 37.2, 36.3, 35.1, 34.7, 34.3, 32,6, 29.6, 28.5, 26.7, 26.6, 26.5, 25.9, 25.8, 25.8, 25.6, 23.8, 22.6, 20.5, 18.0, 16.8, 15.3, 13.1, -4.86, -4.89. Preparation of (7)

To a solution of compound 6 (3.6 g, 3.2 mmol) in dry CH ₂ Cl ₃ (40 mL) was added BF ₃ -Et ₂ O (1.0 mL, 7.3 mmol), and the mixture was stirred at room temperature for 4 h, and TLC (petroleum ether-EtOAc, 1 :1) indicated that the reaction was complete. The mixture was diluted with CH ₂ CIz, washed with satd aq NaHCO ₃ and then satd aq NaCl. The organic layer was combined, dried, and concentrated. Purification by column chromatography (petroleum ether-EtOAc, 1:1) gave 7 as a white foamy solid (3.07 g, 95%): ¹ H NMR (400 MHz, CDCl ₃ ): £8.02-7.27 (m, 20 H ₁ 4 PhCO), 5.89 (t, 1 H, 79.6 Hz ₁ H-3 ^G|C ), 5.67 (t, 1 H ₁ 79.7 Hz, H-4 ^Glc ). 5.53 (dd. 1 H, 77.8, 9.8 Hz, H-2 ^clc ), 4.84 (d, 1 H, 7 7.8 Hz, H-l ^Glc ), 4.62 (dd, 1 H ₁ 7 3.3, 12.0 Hz ₁ H-6a ^Glc ), 4.50 (dd, 1 H, 7 5.1, 12.0 Hz, H-6b ^Glc ), 4.17-4.12 (m, 2 H, H-5 ^Glc , H-3 ^Sat ), 3.88 (dd, 1 H, 7 5.2, 9.4 Hz, H-26a ^So1 ), 3.29 (dd, 1 H, 77.4, 9.3 Hzm H-26b ^Sof ), 0.98 (s,3 H, 19-CH,), 0.94 (d, 3 η, 76.6 Hz, 21 -CZf ₃ ), 0.81 (d, 3 H, 76.6 Hz, 27-CH ₃ ), 0.73 (s, 3 η, 18-CH,). ¹³ C NMR (100 MHz, CDCl ₃ ): δ 218.1, 213.4, 166.0, 165.7, 165.1, 165.0, 133.3, 133.1, 133.0, 133.0, 129.7, 129.6, 129.6,

129.6, 129.5, 129.3, 128.8, 128.8, 128.3, 128.2, 128.2, 101.5, 75.28, 72.9, 72.0, 71.9, 69.9, 66.7, 66.4, 63.2, 60.3, 51.1, 43.2, 42.0, 39.6, 39.5, 39.0, 38.9, 37.1, 36.2, 35.1, 34.6, 33.4, 32.6, 29.5, 29.5, 29.4, 27.7, 26.7, 26.3, 26.3, 23.7, 22.6, 20.5, 19.1, 16.8, 15.2, 14.1, 13.1.

Preparation of (9) To a mixture of compound 8 (1.38 g, 3.08 mraol, J. Org. Chem. 2004, 69, 5497-5500) and 7 (2.6 g, 2.6 mxno!) in anhyd CH ₂ CI ₂ (50 mL) was added NIS (1.04 g, 4.6 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 9 as a foamy solid (2.94 g, 82%): ¹ H NMR (400 MHz, CDCl ₃ ): £8.11-7.28 (m, 30 H, 6 PhCO), 5.90 (t, 1 H, 79.6 Hz, H-3 ^αlc ), 5.67 (t, 1 H, J 9.0 Hz, H-4 ^Glc ), 5.53 (dd, 1 H, J 7.8, 9.8 Hz, H-2 ^Glc ), 5.18 (dd, 1 H, J 3.2, 10.0 Hz, H-3 ^Gl "), 4.84 (d, 1 H, J 7.7 Hz, H-l ^olc ), 4.64-4.48 (m, 4 H, H-6a ^Glc , H-6a ^Gαl , H-6b ^Glc , H-όb ⁰ " ¹ ), 4.48 (d, 1 H, /7.8 Hz, H-l ^Go1 ), 4.23 (br.d, 1 H, J3.0 Hz, H-4 ^α< "), 4.17-4.15 (m, 1 H, H-5 ^Go1 ), 4.10 (br.s, I H, H-3 ^Sm ) _> 4.05 (dd, 1 H, J 1.1, 10.0 Hz ₁ H-5 ^Glc ), 3.96 (t, 1 H, J 6.6 Hz, H-2 ^G| "), 3.88 (dd, 1 H, J 5.2, 9.4 Hz, H-26a ^Snι ), 3.30 (dd, 1 H ₁ J 7.4, 9.3 Hz, H-26b ^Sor ), 0.95 (s, 3 H, 19-Ctfj), 0.94 (d, 3 H, / 7.3 Hz, 2\-CH ₃ ), 0.82 (d, 3 H ₁ / 6.6 Hz ₁ 21-CH ₃ ), 0.73 (s, 3 H, 18-CH ₃ ). Preparation of (12)

To a mixture of compound 10 (685 mg, 1.39 mmol) and 9 (1.6 g, 1.15 mmol) in anhyd CH ₂ Cl ₂ (15 mL) was added Me ₃ SiOTf (26 μL, 0.14 mmol) under N ₂ atmosphere at - 42 ⁰ C. The mixture was stirred under these conditions for 30 min, at which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated to afford a syrup. The syrup was dissolved in pyridine (15 mL) and Ac ₂ O (5 mL) and stirred at room temperature for about 3 h. Then he mixture was concentrated with toluene and purified by column chromatography (petroleum ether-EtOAc, 3:1) to give 12 as a white foamy solid (1.5 g, 75%): ¹ H NMR 400 MHz ₁ CDCl ₃ ): 58.01-7.28 (m, 30 H ₁ 6 PhCO), 5.90 (t, 1 H, J

9.6 Hz, H-3 ^Glel ), 5.67 (t, 1 H ₁ 79.6 Hz, H-4 ^cleI ), 5.58 (dd, 1 H, 73.4, 4.1 Hz, H-4 ^Gol ),5.53 (dd, 1 H, 77.8, 9.7 Hz, H-2 ^Glcl ), 5.30 (dd, 1 H, /3.5, 9.9 Hz, H-3 ^Gal ), 4.99 (t, 1 H, 79.2 Hz, H-3 ^σlcD ), 4.92 (t, 1 H ₁ 79.3 Hz, H-4 ^GlcD ), 4.85 (dd, 1 H, 77.8, 9.8 Hz, H-2 ^GlcD ), 4.84 (d, 1 H, 79.8 Hz, H-l ^0lc0 ), 4.70 (d, 1 H, 77.6 Hz, H-l ^GlcI ), 4.61 (dd, 1 H ₁ 78.8, 12.0 Hz, H-6a), 4.56 (d, 1 H, /7.7 Hz, H-I ⁰ " ¹ ), 4.53-4.48 (m, 2 H, H-όa ¹ , H-6b), 4.36 (dd, 1 H, 77.2, 12.1 Hz, H-6a"), 4.29 (dd, 1 H, J 6.8, 11.1 Hz, H-6b ), 4.19-4.12 (m, 1 H, H-5), 4.10-4.04 (m, 4 H, H-6b", H-3 ^Sar , H-5\ H-2 ^Go1 ), 3.90 (dd, 1 H, 75.2, 9.4 Hz, H-26a ^Sl "), 3.72-3.69 (m, 1 H ₁ H-5"), 3.30 (dd, 1 H, J IA, 9.3 Hz, H-26b ^s ° ^r ), 2.14, 2.08, 1.98, 1.89, 1.75 (5 s, 5 X 3 CH ₃ CO), 0.99 (s, 3 H, 19-CHi) ₁ 0.94 (d, 3 η, 77.3 Hz, 21-CH,), 0.82 (d, 3 η, 76.6 Hz, 27-CHj) ₁ 0.73 (s, 3 η, 18-CH ₃ ). ¹³ C NMR 100 MHz, CDCl ₃ ): J218.0, 213.3, 170.5, 169.9, 169.7, 169.3, 169.2, 166.0, 165.9, 165.7, 165.3, 165.1, 165.0, 133.6, 133.3, 133.2, 133.1,

133.0, 133.0, 129.7, 129.6, 129.6, 129.5, 129.5, 129.5, 129.5, 129.4, 129.4, 129.3, 129.3,

129.1 , 128.8, 128.6, 128.3, 128.3, 128.3, 128.2, 128.2, 101.4, 100.9, 99.5, 75.4, 75.2, 75.1 , 73.9, 72.9, 72.8, 72.0, 71.9, 71.6, 71.1, 70.6, 69.9, 69.5, 68.7, 67.5, 66.4, 63.2, 62.5, 61.8, 60.2, 51.1 , 43.2, 42.0, 41.3, 39.8, 39.5, 39.0, 37.1, 35.9, 34.9, 34.9, 34.6, 32.6, 29.7, 29.6, 26.7, 26.3, 26.2, 26.1, 25.6, 23.7, 22.5, 20.9, 20.7, 20.6, 20.5, 20.4, 20.1 , 16.8, 15.2, 14.1, 13.0.

Preparation of (13)

The mixture of compound 12 (150 rag, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 13 as a white solid (102 mg, 68%): ¹ H NMR (400 MHz, CDCl ₃ ): δ 8.00-7.28 (m, 30 H, 6 PhCO) ₁ 5.88 (t, 1 H ₁ 79.6 Hz, H-3 ^G1cI ), 5.67 (t, 1 H, J9.7 Hz, H-4 ^Glcl ), 5.58 (dd, 1 H, 73.4, 4.1 Hz, H-4° ^Dl ),5.53 (dd, 1 H, 77.8, 9.7 Hz, H-2 ^Glcl ), 5.30 (dd, 1 H, 73.7, 9.8 Hz, H-3 ^Gl "), 5.00 (t, 1 H, 7 9.6 Hz, \i'3 ^GM ), 4.93 (t, 1 H, 7 9.3 Hz ₁ H-4 ^Glςα ), 4.86 (dd, 1 H, 7 7.7, H-2 ^Glc0 ), 4.81 (d, 1 H.77.8 Hz ₁ H-l ^olcO ), 4.70 (d, 1 H, 77.6 Hz, H-l ^Glcl ), 4.61 (dd, 1 H ₁ 73.0, 12.1

Hz, H-6a), 4.55 (d, 1 H, 77.5 Hz, H-I ^Cal ), 4.53-4.51 (m, 2 H, H-6a', H-6b), 4.40 (dd, 1 H, / 7.2, 12.1 Hz, H-6a"), 4.30 (dd, 1 H, /6.8, 11.1 Hz, H-6b'), 4.14-4.03(m, 5 H, H-5, H-6b", H-3 ^Sor , H-5', H-2 ^Go1 ), 3.87 (dd, 1 H, / 5.2, 9.4 Hz, H-26a ^Sθ1 ), 3.75-3.48 (m, 1 H, H-5"), 3.25 (dd, 1 H, / 7.4, 9.3 Hz, H-26b ^Sot ), 2.14, 2.09, 1.98, 1.90, 1.75 (5 s, 5 X 3 CH ₃ CO), 0.99 (s, 3 H, 19-CH,), 0.94 (d, 3 η, / 7.3 Hz, 21-CHj) ₁ 0.80 (d, 3 H, / 6.6 Hz, 27-CHj), 0.73 (8, 3 H ₁ IS-CHj). Preparation of (14)

Compound 13 (100 mg, 0.057 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, v/v, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2: 1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 14 as an amorphous solid (50 mg, 95%): ¹ H NMR (400 MHz, C ₆ D ₅ N): <?5.27 (d, 1 H, / 7.5 Hz, H-l ^GlcD ), 4.91 (d, 1 H ₁ / 7.5 Hz, H-I ⁰ " ¹ ), 4.82 (d, 1 H, / 7.6 Hz, H-l ^σlcI ), 1.15 (d, 3 H, / 6.9 Hz, 21-CH ₃ ), 1.10 (s, 3 η, 19-CHj), 1.02 (d, 3 η, / 6.5 Hz ₁ 27-CH ₃ ), 0.98 (s, 3 η, 18-CH ₃ ). ¹³ C NMR 400 MHz, CD ₅ N): (5110.5, 105.8, 104.9, 102.3, 81.5, 81.0, 78.4, 78.2, 78.2, 77.8, 76.7, 76.4, 75.3, 75.2. 75.1, 75.0, 71.5, 71.5, 69.6, 63.8, 62.6, 62.0, 56.2, 41.0, 40.5, 40.2, 40.1, 36.9, 36.7, 35.3, 35.1, 34.2, 32.2, 30.7, 30.7, 28.1, 26.8, 26.6, 26.6, 23.8, 21.0, 17.3, 16.5, 16.3. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ⁺ ; Found 944.0 [M + Na] ⁺ .

Example 2

The preparation of (25S)-26-0-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3β, 26-diol- 3-O-β-D- galactopyranoside (18) The overall reaction scheme is as follows:

Patent-scheme2

Preparation of (16) To a mixture of compound 15 (2.03 g, 3.10 mmol, commercially available) and 7

(2.6 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was added NIS (1.05 g, 4.7 mmol), Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under r.t, for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 2:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 16 as a foamy solid (3.72 g, 90%): MALD1TOF-MS: Calcd for C ₉₅ H ₉₆ O ₂₂ : 1588.64 [M]"; Found 1611.5 [M + Na] ⁺ . Preparation of (17)

The mixture of compound 16 (600 mg, 0.38 mmol) and NaBH ₄ (357 mg, 9.4 mmol) in 2-propanol (16 mL) and CH ₂ Cl ₂ (2 mL) was stirred at room temperature for about 7.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 17 as a white solid (393 mg, 65%): Calcd for C ₉₅ H ₉₈ O ₂₂ : 1590.65 [M] ⁺ ; Found 1613,5 [M + Na] ⁺ . Preparation of (18) Compound 17 (210 mg, 0.13 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2,

24 mL), and then 1.0 M NaOMe in MeOH (0.25 raL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₃ O, 2:0.5:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H'), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 18 as an amorphous solid (94 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): «55.35 (d, 1 H, Jl.5 Hz, H-l ^GlcD ), 5.00 (d, 1 H, /8.0 Hz, H-I ⁰ "'), ¹³ C NMR 100 MHz, CD ₅ N): δ 104.9 (C-I), 102.3 (C-I). MALDITOF-MS: Calcd for C ₃₉ H ₆₆ O ₁₄ : 758.45 [M] ⁺ ; Found 781.31 [M + Na] ⁺ .

Example 3

The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furoslane-3β, 26- diol-3-O-β-D- glucopyranoside (21) The overall reaction scheme is as follows:

Patent-scheme3

Preparation of (19)

To a mixture of compound 10 (1.54 g, 3.12 mmol) and 7 (2.6 g, 2.6 mmol) in anhyd

CH ₂ Cl ₂ (30 mL) was added Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under room temperature for 15 min, at the end of which time

TLC (petroleum ether-EtOAc, 2:1) indicated that all starting materials were consumed.

The reaction mixture was neutralized with TEA, then concentrated. Column

chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 19 as a foamy solid (2.96 g, 85%): MALDITOF-MS: Calcd for C ₇₅ H ₈₈ O ₂₃ : 1340.58 [M] ⁺ ; Found 1363.70 [M + Na] ⁺ .

Preparation of (20) The mixture of compound 19 (114 mg, 0.085 mmol) and NaBRi (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Ch (1 ∞L) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ CI ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 20 as a white solid (74 mg, 65%): MALDITOF-MS: Calcd for C ₇₅ H ₉₀ O ₂₂ : 1342.59 [M] ⁺ ; Found 1365.60 [M + Na] ⁺ . Preparation of (21) Compound 20 (70 mg, 0.052 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, v/v, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5.5 h, TLC (U-BuOH-EtOH-H ₂ O, 2:0.5:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 21 as an amorphous solid (38 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.36 (d, 1 H, J 7.5 Hz, H-l ^Glc "), 5.20 (d, 1 H.77.9 Hz, H-l ^Gal ), ¹³ C NMR 100 MHz ₁ CD ₅ N): £ 105.1 (C-I), 103.8 (C-I). MALDITOF-MS: Calcd for C ₃₉ H ₆₆ O ₁₄ : 758.45 [M] ⁺ ; Found 781.31 [M + Na] ⁺ .

Example 4 The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3β, 26- diol-3-0-β-D-glucopyranosyl-(l→4) -β-D -galactopyranoside (26) The overall reaction scheme is as follows:

Patent-scherae4

Preparation of (24) To a mixture of compound 10 (2.5 g, 5.1 mmol, commercially available from Beijing

Carboraex Biotech Co., Ltd.) and 22 (2.55 g, 4.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 0C was added TMSOTf (92 μL, 0.51 mmol). The mixture was stirred at these conditions for 1 h, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 23 (3.36 g, 83%). To a mixture of 23 (3.1 g, 3.52 mmol) and 7 (3.24 g, 3.2 mmol) in anhyd CH ₂ Cl ₂ (55 mL) at -20 ⁰ C was added NIS (1.18 g, 5.28 mmol) and Me ₃ SiOTf (63 μL, 0.35 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:2) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 24 as a foamy solid (4.94 g, 85%): MALDITOF-MS: Calcd for C _1O2 Hi ₁₀ O _3I ): 1814.71 [M] ⁺ ; Found 1837.50 [M + Na] ^* .

Preparation of (25)

The mixture of compound 24 (500 mg, 0.275 mmol) and NaBIi, (313 mg, 8.26

mmol) in 2-propanol (24 mL) and CH ₂ Cl ₂ (3 mL) was stirred at room temperature for about 8.5 b. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 25 as a white solid (320 mg, 64%): MALDITOF-MS: Calcd for CIO ₂ H ₁ I ₂ O ₃₀ : 1816.72 [M] ⁺ ; Found 1839.50 [M + Na] ⁺ . Preparation of (26) Compound 25 (200 mg, 0.11 mmol) was dissolved in anliyd CH ₂ Cl ₂ - MeOH (1:2, v/v, 21 mL), and then 1.0 M NaOMe in MeOH (0.22 mL) was added at 0 ⁰ C. After stirring at room temperature for 4.5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 26 as an amorphous solid (95 mg, 94%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.36 (d, 1 H, 77.5 Hz, H-I), 5.30 (d, 1 H, J7.5 Hz, H-I), 5.20 (d, 1 H, / 7.9 Hz, H-I) ₁ ¹³ C NMR 100 MHz, CD ₅ N): δ 105.1 (C-I), 103.8 (C-I), 102.5 (C-I). MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ⁺ ; Found 943.7 [M + Na]' .

Example 5 The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3β, 26- diol-3-O-β-D-glucopyranosyl-(l →2)-β-D-glucopyranoside (31) The overall reaction scheme is as follows:

Patent-scheme5

Preparation of (28) To a mixture of compound 27 (1.57 g, 2.86 mmol, J. Org. Chem. 2004, 69,

5497-5500) and 7 (2.6 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (35 mL) was added NIS (643 mg, 2.86 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 rain, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 28 as a foamy solid (3.09 g, 80%). MALDITOF-MS: Calcd ^w C ₈₈ H ₉₂ O _2I : 1484.61 [M] ⁺ ; Found 1507.80 [M + Na] ⁺ . Preparation of (29) To a mixture of compound 10 (834 mg, 1.69 mmol) and 28 (2.1 g, 1.41 mmol) in anhyd CH ₂ Cl ₂ (18 mL) was added Me ₃ SiOTf (31 μL, 0.17 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 20 min, at which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated to afford 29 as a white

foamy solid (2.0 g, 78%). MALDITOF-MS: Calcd for C _1O iHi _1O O ₃₀ : 1814.71 [M] ⁺ ; Found 1837.8 [M + Na] ⁺ .

Preparation of (30)

The mixture of compound 29 (600 mg, 0.33 mmol) and NaBH ₄ (312 mg, 8.25 mmol) in 2-propanol (24 mL) and CH ₂ Cl ₂ (3 mL) was stirred at room temperature for about 6.5 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₃ SOj, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 : 1) to give compound 30 as a while solid (313 mg, 67%). MALDITOF-MS: Calcd for C ₁₀₂ HM ₂ O ₃₀ : 1816.71 [M] ⁺ ;

Found 1839.8 [M + Na] ⁺ .

Preparation of (31)

Compound 30 (200 mg, 0.14 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2,

27 mL), and then 1.0 M NaOMe in MeOH (0,3 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column Io afford 31 as an amorphous solid (122 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.36 (d, 1 H,

77.8 Hz, H-I), 5.30 (d, 1 H ₁ 77.5 Hz, H-I), 5.20 (d, 1 H, 77.9 Hz, H-I) ₁ ¹³ C NMR 100 MHz, CD ₅ N): δ 104.9 (C-I), 103.5 (C-I) ₁ 102.1 (C-I). MALDITOF-MS: Calcd for

C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ⁺ ; Found 944.0 [M + Na] ⁺ .

Example 6

The preparation of (25S)-26-O-β-D-gmcopyranosyl-22-hydroxy-5β-furostane-3β,2 6- diol-3-0-β-D-glucopyranosyl-(l→4)-β-D-glucopyτanoside (36) The overall reaction scheme is as follows:

Patent-schemeό

Preparalion of (34)

To a mixture of compound 32 (3.1 g, 5.78 mmol, J. Org. Chem, 2004, 69, 5497-5500) and 5 (5.14 g, 6.94 mmol) in anhyd CH ₂ Cl ₂ (60 raL) at O ⁰ C was added TMSOTf (126 μL, 0.70 mmol). The mixture was stirred at these conditions for 0.5 h, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 33 (5.8 g, 90%). To a mixture of 33 (2,0 g, 1.8 mmol) and 7 (1.66 g, 1.64 mmol) in anhyd CH ₂ Cl ₂ (30 mL) was added NlS (607 rag, 2.7 mmol) and Me ₃ SiOTf (33 μL, 0.18 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under room temperratυre for 30 rain, at the end of which time TLC (petroleum ether-EtOAc, 2: 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 34 as a foamy solid (2.88 g, 85%). MALDITOF-MS: Calcd for C ₁₂₂ H ₁₁₈ O _3U : 2062.77 [M]'; Found 2085.90 [M + Na] ⁺ . Preparation of (35)

The mixture of compound 34 (175 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 tnLX2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 35 as a white solid (120 mg, 68%). MALDITOF-MS: Calcd for C ₁₂₂ H ₁₂₀ O ₃₀ : 2064.77 [M] ⁺ ; Found 2087.90 [M + Na] ⁺ . Preparation of (36)

Compound 35 (120 mg, 0.057 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.21 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 b, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 36 as an amorphous solid (50 rag, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.36 (d, 1 H, 77.8 Hz, H-I), 5.30 (d, 1 H, 77.5 Hz, H-I), 5.20 (d, 1 H, J 7.9 Hz, H-I), ¹³ C NMR 100 MHz, CD ₅ N): δ 104.9 (C-I), 103.5 (C-I), 102.1 (C-I). MALDITOF-MS: Calcd for C ₄₅ H ₇₆ Oi ₉ : 920.50 [M] ⁺ ; Found 943.90 [M + Na] ⁺ .

Example 7

The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-turostane-3β, 26- diol-3-O-β-D-glucopyτanosyl-(l→6)-β-D-glucopyranoside (41) The overall reaction scheme is as follows:

Patenl-scheme7

Preparation of (39) To a mixture of compound 10 (2.5 g, 5.07 mmol) and 37 (2.47 g, 4.61 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at O ⁰ C was added TMSOTf (92 μL, 0.51 mmol). The mixture was stirred at these conditions for 20 rain, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 38 (3.67 g, 92%). To a mixture of 38 (2.1 g, 2.4 mmol) and 7 (2.02 g, 2.0 mmol) in anhyd CH ₂ Cl ₂ (35 mL) at -20 "C was added NIS (810 mg, 3.6 mmol) and Me ₃ SiOTf (43 μL, 0.24 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 39 as a foamy solid (2.98 g, 82%). MALDITOF-MS: Caicd for Ci _O2 Hi ₁₀ O _3O : 1814.71 [M] ⁺ ; Found 1837.8 [M + Na] ⁺ . Preparation of (40)

The mixture of compound 39 (154 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propaDθl (8 mL) and CH)Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mL X 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 40 as a white solid (99 mg, 64%). MALDITOF-MS: Calcd for Ci ₀₂ H ₁₁₂ O ₃₀ : 1816.71 [M] ⁺ ; Found 1839.8 [M + Na] ⁺ . Preparation of (36) Compound 40 (80 rag, 0.056 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2,

18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 41 as an amorphous solid (50 mg, 96%): ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.31 (d, 1 H, J 7.5 Hz, H-I), 5.28 (d, 1 H, J 7.5 Hz, H-I), 5.19 (d, 1 H ₁ J 7.6 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): 5105.0, 103.5, 102.1. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ⁺ ; Found 943.8 [M + Na] ⁺ .

Example 8

The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3β, 26- diol-3-O-α-L- rhamnopyranosyl -(l-»2)-β-D-glucopyranoside (45) The overall reaction scheme is as follows:

Patent-schemeδ

Preparation of (43) To a mixture of compound 42 (1.5 g, 2.4 mmol, commercially available) and 28

(3.27 g, 2.2 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added TMSOTf (44 μL, 0.24 mmol). The mixture was stirred at these conditions for 40 min, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 43 (3.68 g, 86%). MALDITOF-MS: Calcd for CHSH,, ₄ O ₂₈ : 1942.75 [M] ⁺ ; Found 1965.60 [M + Na] ⁺ .

Preparation of (44)

The mixture of compound 43 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CHjCi ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ CI ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ Sθ ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 44 as a white solid (115 mg, 70%). MALDITOF-MS: Calcd for C ₁₁₅ Hn ₆ O ₂₈ : 1944.75 [M] ⁺ ; Found 1967.60 [M + Na] ⁺ . Preparation of (45)

Compound 44 (100 mg, 0.051 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2,

18 QiL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After sthτing at room temperature for 5 h, TLC (n-BuOH-EtOH-HA 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H'), and then filtered and concentrated. The residue was purified by Bio-gel Pi column to afford 45 as an amorphous solid (44 rag, 95%): ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.49 (d, 1 H, /3.5 Hz, H-I), 5.25 (d, 1 H, J 7.5 Hz, H-I), 5.09 (d, 1 H, J 7.9 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 106.8, 104.0, 102.1. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 947.80 [M + Na] ⁺ .

Example 9

The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3β, 26- diol-3-O-α-L- rhamnopyranosyl -(l→4)-β-D-glucopyranoside (49) The overall reaction scheme is as follows:

Patent-scheme9

Preparation of (47)

To a mixture of compound 32 (2.1 g, 3.9 mmol, commercially available) and 42

(2.85 g, 4.6 mmol) in anliyd CH ₂ Cl ₂ (45 mL) al -20 ⁰ C was added TMSOTf (83 μL, 0.46 mmol). The mixture was stirred at these conditions for 30 rain, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 46 (3.57 g, 92%). To a mixture of 46 (2.1 g, 2.11 mmol) and 7 (1.94 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (45 mL) at -20 ⁰ C was added NIS (712 mg, 3.2 mmol) and Me ₃ SiOTf

(38 μL, 0.211 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 47 as a foamy solid (3.17 g, 85%). M ALDlTOF-MS: Calcd for

C|i ₅ H _{1 M} O ₂₈ : 1942.75 [M] ⁺ ; Found 1965.60 [M + Na] ⁺ .

Preparation of (48)

The mixture of compound 47 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 48 as a white solid (115 mg, 70%). MALDITOF-MS: Calcd for CsHn ₆ O ₂₈ : 1944.75 [M] ⁺ ; Found 1967.60 [M + Na] ⁺ . Preparation of (49)

Compound 48 (100 mg, 0.051 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 rnL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2: 1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 49 as an amorphous solid (44 mg, 95%). MALDITOF-MS: Calcd for C ₄₃ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 947.80 [M + Na] ⁺ .

Example 10

The preparation of (25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-rurostane-3β, 26- diol-3-O-α-L- rhamnopyranosyl-(l→6)-β-D-galactopyranoside (54) The overall reaction scheme is as follows:

Patent-scheme 10

Preparation of (52) To a mixture of compound 50 (2,1 g, 3.9 ramol, commercially available from Beijing

Carbomex Biotech Co. Ltd.) and 42 (2.85 g, 4.6 mraol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added TMSOTf (83 μL, 0.46 mmol). The mixture was stirred at these conditions for Ih ₁ then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 51 (3.69 g, 95%). To a mixture of 51 (2.1 g, 2.11 mmol) and 7 (1.94 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (40 mL) at -20 ⁰ C was added NIS (712 mg, 3.2 mmol) and Me ₃ SiOTf (38 μL, 0.211 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC

(petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of die residue gave 52 as a foamy solid (3.17 g, 85%). MALDITOF-MS: Calcd for C ₁₁₅ H _{1 M} O ₂₈ : 1942.75 [M] ⁺ ; Found 1965.60 [M + Na] ⁺ . Preparation of (53)

The mixture of compound 52 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CHjCl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₃ Cl: (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 53 as a white solid (115 mg, 68%). MALDITOF-MS: Calcd for C ₁₁₅ Hu ₆ O ₂₈ : 1944.75 [M] ⁺ ; Found 1967.60 [M + Na] ⁺ . Preparation of (54) Compound 53 (100 mg, 0.057 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2,

18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 54 as an amorphous solid (44 mg, 95%): ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.37 (d, 1 H, J 2.5 Hz, H-I), 5.24 (d, 1 H, J 7.5 Hz, H-I), 5.18 (d, 1 H, J 7.6 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 104.1, 102.5. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 947.80 [M + Na] ⁺ .

Example 11

The preparation of

(25S)-26-0-β-D-gIucopyranosyl-22-hydroxy-5β-furostane-3 β,26-dio]-3-0-[α-L- rhamnopyranosyl-(l →2)]-[α-L- rhamnopyranosyl-(l-→6)]-β-D-glucopyranoside (59) The overall reaction scheme is as follows:

Patent-scheme 11

Preparation of (56)

To a mixture of 55 (996 mg, 2.30 mmol) and 7 (1.94 g, 1.92 mmol) in anliyd CH ₂ Cl ₂ (20 mL) at -40 ⁰ C was added NIS (517 mg, 2.30 mmol) and Me ₃ SiOTf (42 μL, 0.23 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 56 as a foamy solid (2.12 g, 80%). MALDITOF-MS: Calcd for C ₈₁ H ₈₈ O ₂₀ : 1380.59 [M] ⁺ ; Found 1403.70 [M + Na] ⁺ .

Preparation of (57)

To a mixture of 56 (2.0 g, 1.45 mmol) and 42 (2.16 g, 3.48 mmol) in anliyd CH ₂ Cl ₂

(30 mL) at -20 ⁰ C was added Me ₃ SiOTf (62 μL, 0.34 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:1) indicated that all starting materials were consumed. The reaction mature was neutralized with TEA, lhen concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 57 as a foamy solid (2.83 g, 85%). MALDITOF-MS: Calcd for Ci ₃₅ H ₁₃₂ O ₃₄ : 2296.86 [M] ⁺ ; Found 2319.90 [M + Na] ⁺ .

Preparation of (58)

The mixture of compound 57 (195 mg, 0.085 mmol) and NaBR, (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 58 as a white solid (121 mg, 68%). MALDITOF-MS: Calcd for C ₁₃₅ H ₁₃₄ O ₃₄ : 2298.86 [M] ⁺ ; Found 2321.90 [M + Na] ⁺ . Preparation of (59)

Compound 58 (120 mg, 0.052 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2: 1 :1) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin Qi ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 59 as an amorphous solid (53 mg, 97%): Selected ¹ H NMR (400 MHz, C ₆ D ₃ N): £5.46 (d, 1 H, 72.5 Hz, H-I), 5.41 (d, 1 H, 72.4 Hz, H-I), 5.09 (d, 1 H, 77.5 Hz, H-I), 5.00 (d, 1 H ₁ J 7.6 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 108.5, 105.1, 102.9, 102.3. MALDITOF-MS: Calcd for C _5I H ₈₆ O ₂₂ : 1050.56 [M] ⁴ ; Found 1073.80 [M + Na] ⁺ .

Example 12

The preparation of

(25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3 p,26-diol-3-O-[β-D- gIucopyranosyl-(l→4)3-[α-L- rhamnopyranosyl-(l→2)]-β-D-glucopyranoside (62) The overall reaction scheme is as follows:

56

= =

62 R ¹ = R ² = H

R ² O OR ²

Patent-scheme 12

Preparation of (60)

To a mixture of compound 56 (2.5 g, 1.81 mraol) and 42 (1.35 g, 2.17 mrnol) in anhyd CH ₂ Cl ₂ (50 nαL) at -40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at these conditions for 40 min, then the mixture was added 10 (1.07 g, 2.17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at O ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum etber-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 60 as a foamy solid (3.1O g, 79%).

MALDITOF-MS: Calcd for C ₁₂₂ Hi ₂₈ O ₃₆ : 2168.82 [Mf; Found 2192.0 [M + Na] ⁺ .

Preparation of (61)

The mixture of compound 60 (185 mg, 0.085 mmol) and NaBH, (96 mg, 2.5 mmol)

in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SOi, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 : 1) to give compound 61 as a white solid (118 mg, 64%). MALDITOF-MS: Calcd for C ₁₂₂ H ₁₃₀ O ₃₆ : 2170.82 [M] ⁺ ; Found 2194.0 [M + Na] ⁺ . Preparation of (62) Compound 61 (100 mg, 0.046 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 62 as an amorphous solid (47 mg, 95%). MALDITOF-MS: Calcd for C ₅ iH _β6 O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.72 [M + Na] ⁺ .

Example 13

The preparation of

(25S)-26-0-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3 β,26-diol-3-0-[α-L- rhamnopyranosyl-(l →4)]-[β-D-glucopyranosyl-(l →2)]-β-D-gIucopyranoside (65) The overall reaction scheme is as follows:

Patent-scheme 13 Preparation of (63)

To a mixture of compound 56 (2.5 g, 1.81 mmol) and 5 (1.61 g, 2.17 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at - 40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at these conditions for 40 min, then the mixture was added 42 (1.35 g, 2.17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at O ⁰ C. The mixture was stirred under these conditions for 30 rain, at the end of which time TLC (petroleum ether-EtOAc,

1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 63 as a foamy solid (3.46 g, 79%).

MALDITOF-MS: Calcd for C ₁₄₂ H ₁₃₆ O ₃₆ : 2416.88 [M] ⁺ ; Found 2439.75 [M + Na] ⁺ .

Preparation of (64)

The mixture of compound 63 (206 mg, 0.085 mmol) and NaBH ₄ (96 ing, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₃ SO.), and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 64 as a white solid (123 mg, 60%). MALDITOF-MS: Calcd for C _H aHi ₃₈ O ₃₆ : 2418.88 [M]';

Found 2441.75 [M + Na] ⁺ . Preparation of (65) Compound 64 (120 mg, 0.050 mmol) was dissolved in aπhyd CH ₂ Cl ₂ - MeOH (1 :2,

18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized wilb ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 65 as an amorphous solid (51 mg, 95%). MALDITOF-MS: Calcd for CsiHs^ 1066.56 [M] ⁺ ;

Found 1089.72 [M + Na] ⁺ .

Example 14

The preparation of

(25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3 β,26-diol-3-O-[β-D-glucopyr anosyl-(l→4)]-[α-L- rhamnopyranosyl -(l-»2)]-β-D-galaclopyranoside (68) The overall reaction scheme is as follows:

Patent-schemel4

Preparation of (66)

To a mixture of compound 9 (2.5 g, 1.81 mmol) and 42 (1.35 g, 2.17 mmol) in anhyd

CH ₂ Cl ₂ (50 mL) at - 40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at these conditions for 40 min, then the mixture was added 5 (1.61 g, 2.17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum erher-EtOAc, 2:1) of the residue gave 66 as a foamy solid (3.46 g, 79%). MALDITOF-MS: Calcd for C _H2 H ₁₃₆ O ₃₆ : 2416.88 [M] ⁺ ; Found 2439.75 [M + Na] ⁺ . Preparation of (67) The mixture of compound 66 (206 mg, 0.085 mmol) and NaBR ₁ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h. The reaction mixture was then extracted with CH ₂ Cb (100 mLX2), the combined organic layer was washed with water (100 mLX3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 67 as a white solid (123 mg, 60%). MALDITOF-MS: Calcd for C ₁₄₂ H ₁₃₈ O ₃₆ : 2418.88 [M] ⁺ ; Found 2441.75 [M + Na] ⁺ . Preparation of (68) Compound 67 (120 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0,5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 66 as an amorphous solid (49 mg, 93%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.50 (d, 1 H, 72.7 Hz, H-I), 5.37 (d, 1 H, /7.2 Hz, H-I), 5.04 (d, 1 H, J 7.3 Hz, H-I), 5.00 (d, 1 H, J 1.9 Hz, H-I). ¹³ C NMR (100 MHz ₁ CDjN): δ 107.5, 105.1 , 102.9, 102.1. MALDITOF-MS: Calcd for Cj ₁ H ₈₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.72 [M + Na] ⁺ .

Example IS

The preparation of

(ISSJ^δ-O-β-D-glucopyranosyl^-hydroxy-Sβ-ftirostane-S� �^β-diol-S-O-fα-L- rhamnopyraπosyl-(l →4)]-[β-D-glucopyranosyl-(l-→2)]-β-D-galactopyranoside (71) The overall reaction scheme is as follows:

Patent-scheme 15

Preparation of (69)

To a mixture of compound 9 (2,5 g, 1.81 mmol) and 5 (1.61 g, 2.17 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at - 40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at these conditions for 40 min, then the mixture was added 42 (1.35 g, 2,17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc,

1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 69 as a foamy solid (3.46 g, 79%).

MALDITOF-MS: Calcd for C ₁₄₂ H ₁₃₆ O ₃₆ : 2416.88 [M] ⁺ ; Found 2439.75 [M + Na] ⁺ .

Preparation of (70)

The mixture of compound 69 (206 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX2), the combined organic layer was washed with water (100 mJLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 70 as a white solid (123 mg, 60%). MALDITOF-MS: Calcd for CH ₂ H ₁₃₈ O ₃₆ : 2418.88 [M] ⁺ ; Found 2441.75 [M + Na] ⁺ . Preparation of (71)

Compound 70 (120 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 inL), and then 1.0 M NaOMe in MeOH (0.2 raL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (1-I ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 71 as an amorphous solid (49 mg, 93%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.51 (d, 1 H, J 2.7 Hz, H-I), 5.32 (d, 1 H, ./ 7.2 Hz, H-I), 5.05 (d, 1 H, / 7.3 Hz, H-I) ₁ 5.02 (d, 1 H, J 7.9 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): S 107.5, 104.0, 103.2, 102.0. MALDITOF-MS: Calcd for Cj|H ₈₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.72 [M + Na] ⁺ .

Example 16

The preparation of (25S)-26-0-p-D-glucopy _T anosyl-22-hydroxy-5p-furostane-3p,26-diol-3-0-p-D-glucopyr anosyl-(l →4)-P-D-glucopyranosyl-(l -»4)-p-D-galactopyτanoside (76) The overall reaction scheme is as follows:

Patent-scheme 16

Preparation of (74)

To a mixture of compound 72 (2.5 g, 3.20 mmol) and 22 (1.60 g, 2.91 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added TMSOTf (58 (.iL, 0.32 mmol). The mixture was stirred at these conditions for 40 rain, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 73 (2.93 g, 86%). To a mixture of 73 (2.0 g, 1.7 mmol) and 7 (1.57 g, 1.55 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added NIS (562 mg, 2.5 mmol) and Me ₃ SiOTf (31 μL, 0.17 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated, Column chromatography (petroleum ether-ElOAc, 2:1) of the residue gave 74 as a foamy solid (2.71 g, 83%). MALDITOF-MS: Calcd for C ₁₁₄ H ₁₂₆ O ₃₈ : 2102.79 [M] ⁺ ; Found 2125.90 [M + Na]*.

Preparation of (75)

The mixture of compound 74 (179 mg, 0.085 rπmol) and NaBH., (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 75 as a white solid (116 mg, 67%). M ALDITOF-MS: Calcd for CnH ₁₂₈ O _3B : 2104.79 [M] ⁺ ; Found 2127.90 [M + Na] ⁺ . Preparation of (76)

Compound 75 (100 mg, 0.047 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁴ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 76 as an amorphous solid (49 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): <? 5.35 (d, 1 H, 77.2 Hz, H-I), 5.31 (d, 1 H, J 7.2 Hz, H-I), 5.10 (d, 1 H, J 7.3 Hz, H-I), 5.00 (d, 1 H, J 8.0 Hz, H-I). ¹³ C NMR (100 MHz ₁ CD ₅ N): δ 105.1, 103.4, 102.9, 101.3. MALDITOF-MS: Calcd for C _5I H ₈₆ O ₂₄ : 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺ .

Example 17 The preparation of

(25S)-26-O-β-D-glucopyranosyl-22-hydroxy-5β-furostane-3 β,26-diol-3-O-β-D-glucopyr anosyl-( 1 →4)-β-D-glucopyranosyl-( 1 →2)-β-D-galactopyranoside (79) The overall reaction scheme is as follows:

Patent-schemel?

Preparation of (77)

To a mixture of compound 72 (2.5 g, 3.20 mmol) and 9 (4.02 g, 2.91 ramol) in anhyd CH ₂ Cl ₂ (50 mL) at -40 ⁰ C was added TMSOTf (58 μL, 0.32 mmol). The mixture was stirred at these conditions for 1 h, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 77 (4.54 g, 78%).

MALDγγOF-MS: Calcd for C ₁₀₇ H ₁₂₂ O ₃₇ : 1998.77 [M] ⁺ ; Found 2021.90 [M + Na] ⁺ .

Preparation of (78) The mixture of compound 77 (170 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ CIi 0 mL) was stirred at room temperature for about 8,5 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 78 as a white solid (116 mg, 68%). MALDITOF-MS: Calcd for Ci ₀₇ H ₁₂₄ O ₃₇ : 2000.77 [M] ⁺ ;

Found 2023.90 [M + Naf .

Preparation of (79)

Compound 78 (100 mg, 0.05 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2,

18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added al 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2: 1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 79 as an amorphous solid (51 mg, 94%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.34 (d, 1 H, 77.5 Hz, H-I) ₁ 5.18 (d, 1 H, J 1.2 Hz, H-I) ₁ 5.08 (d, 1 H ₁ J l.l Hz, H-I ) ₁ 5.05 (d, 1 H, J 7.9 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.1, 102.9, 101.9. MALDITOF-MS: Calcd for C ₅₁ H ₈₆ O ₂ ,,: 1082.55 [M]*; Found 1105.70 [M + Na] ⁺ .

Example 18

The preparation of

(25S)-26-0-β-D-glucopyranosyl-22-hydroxy-5β-flιrostane -3p,26-diol-3-0-β-D-glucopyr anosyl-(l ~»4)-β-D-glucopyranosyl-(l →4)-β-D-glucopyranoside (83) The overall reaction scheme is as follows:

R H

Patent-schemelδ

Preparation of (81)

To a mixture of compound 32 (2.1 g, 3.9 mmol) and 72 (3.6 g, 4.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added TMSOTf (83 μL, 0.46 mmol). The mixture was stirred at these conditions for30 min, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 80 (4.14 g, 92%). To a mixture of 80 (2.5 g, 2.16 mmol) and 7 (1.98 g, 1.96 mmol) in anhyd CH ₃ Cl ₂ (50 mL) at -20 ⁰ C was added NIS (729 mg, 3.24 mmol) and Me ₃ SiOTf (40 μL, 0.22 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 1 :1) of the residue gave 81 as a foamy solid (3.51 g, 85%). MALDITOF-MS: Calcd for C ₁₁₄ Hi ₂₆ O ₃₈ : 2102.79 [M] ⁺ ; Found 2125.90 [M + Na] ⁺ .

Preparation of (82) The mixture of compound 81 (179 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 raLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 : 1) to give compound 82 as a white solid (116 mg, 67%). MALDITOF-MS: Calcd for CuHi ₂₈ O ₃ B: 2104.79 [M]'; Found 2127.90 [M + Na] ¹ . Preparation of (83)

Compound 82 (100 mg, 0.047 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ^"1 ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 83 as an amorphous solid (49 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.29 (d, 1 H,

J 1.5 Hz, H-I), 5.20 (d, 1 H, 77.2 Hz ₁ H-I), 5.11 (d, 1 H, /7.5 Hz, H-I), 5.05 (d, 1 H, J 8.0 Hz, H-I). ¹³ C NMR (100 MHz ₁ CD ₅ N): δ 104.3, 103.0, 102.9, 101.0. MALDITOF-MS: Calcd for Cj ₁ H ₈₆ O ₂ ,,: 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺ .

Example 19

The preparation of

(25S)-26-0-P-D-glucopyranosy ^] -22-hydroxy-5β-nιrostane-3p,26-diol-3-0-p-D-glucopyr anosyl-( 1 →4)-β-D-glucopyranosyl -( 1 →2)-β-D-glucopyranoside (86) The overall reaction scheme is as follows:

Patent-scheme 19

Preparation of (84)

To a mixture of compound 28 (5.8 g, 3.9 mmol) and 72 (3.6 g, 4.6 mmol) in anhyd CH ₂ Cl ₂ (55 mL) at -20 ⁰ C was added TMSOTf (83 μL, 0.46 mmol). The mixture was stirred at these conditions for 30 min, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 84 (4.14 g, 92%). (6.97 g, 85%). MALDITOF-MS: Calcd for C _{1 Pt} H] ₂₆ O ₃₈ : 2102.79 [M] ⁺ ; Found 2125.90 [M + Na] ⁺ .

Preparation of (85) The mixture of compound 84 (179 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol)

in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred al room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 85 as a white solid (116 mg, 67%). MALDITOF-MS: Calcd for C ₁₁₄ Hi ₂₈ O ₃₈ : 2104.79 [M] ⁺ ; Found 2127.90 [M + Na] ⁺ . Preparation of (86) Compound 85 (100 mg, 0.047 mmol) was dissolved in anliyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-Bu0H-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 86 as an amorphous solid (50 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.24 (d, 1 H, J 7.5 Hz ₁ H-I), 5.11 (d, 1 H, J 7.2 Hz, H-I), 5.10 (d, 1 H, J 1.1 Hz ₁ H-I), 5.09 (d, 1 H, J 7.9 Hz, H-I). ¹¹ C NMR (100 MHz, CD ₅ N): δ 103.5, 103.3, 102.9, 101.0. MALDITOF-MS: Calcd for C _5I H ₈₆ O ₂₄ : 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺

Example 20 The preparation of

(25S)-26-O-β-D-galactopyranosyl-22-hydroxy-5p-rurostane- 3β,26-diol-3-O-P-D- galactopyranoside (92) The overall reaction scheme is as follows:

Pateπt-scheme20

Preparation of (89) To a mixture of compounds 4 (2.25 g, 4.1 mraol) and 87 (3.56 g, 4.8 mmol, commercially available) in anhyd CH ₂ Cl ₂ (36 mL) was added Me ₃ SiOTf (86 μL, 0.47 mmol) under N ₂ atmosphere at - 20 ^U C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 4:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with triethylamine (TEA), then concentrated. Column chromatography (petroleum ether-EtOAc, 6:1) of the residue gave 88 as a foamy solid (3.7 g, 80%). Tb a solution of compound 88 (3.6 g, 3.2 ramol) in dry CH ₂ Cl ₂ (40 mL) was added BF ₃ -Et ₂ O (1.0 mL, 7.3 mmol), and the mixture was stirred at room temperature for 4 h, and TLC (petroleum ether-EtOAc, 1 :1) indicated that the reaction was complete. The mixture was diluted with CH ₂ Cl ₂ , washed with satd aq NaHCO ₃ and then satd aq NaCI. The organic layer was combined, dried, and concentrated. Purification by column chromatography (petroleum ether-EtOAc, 1 :1) gave 89 as a white foamy solid (3.07 g, 95%): MALDITOF-MS: Calcd for C ₆ )H ₇₀ O ₁₃ : 1010.48 [M] ⁺ ; Found 1033.60 [M + Na] ⁺ Preparation of (90) To a mixture of compound 87 (2.30 g, 3.10 mmol) and 89 (2.6 g, 2.6 mmol) in anhyd

CH ₂ Cl ₂ (50 mL) was adde Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at 0 ⁰ C.

The mixture was stirred under r.t. for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 2: 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum etber-EtOAc, 2:1) of the residue gave 90 as a foamy solid (3.72 g, 90%): MALDITC ⁾ F-MS: Calcd for C ₉₅ H ₉₆ O ₂₂ : 1588.64 [M] ⁺ ; Found 1611.5 [M + Na] ⁺ . Preparation of (91)

The mixture of compound 90 (600 mg, 0.38 mmol) and NaBH ₄ (357 mg, 9.4 mmol) in 2-propanol (16 raL) and CH ₂ Cl ₂ (2 mL) was stirred at room temperature for about 7.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX3) and dried over anhydrous Na ₂ SCM, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1 ) to give compound 91 as a white solid (393 mg, 65%): Calcd for C ₉₅ H ₉₈ O ₂₂ : 1590.65 [M] ⁺ ; Found 1613.5 [M + Naf.

Preparation of (92) Compound 91 (210 mg, 0.13 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 24 mL), and then 1.0 M NaOMe in MeOH (0.25 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:0,5:0.5) indicated thai the reaction was complete. The solution was neutralized witli ion-exchange resin (H ⁺ ), and then filtered and concentrated, The residue was purified by Bio-gel P ₂ column to afford 92 as an amorphous solid (94 mg, 95%); Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.37 (d, 1 H, J 7.5 Hz, H-I), 5.20 (d, 1 H, J 7.2 Hz, H-I . ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.1. MALDITOF-MS: Calcd for C ₃₉ H ₆₆ O ₁₄ : 758.45 [M] ⁺ ; Found 781.31 [M + Na]\

Example 21 The preparation of

(25S)-26-O-β-D-galactopyranosyl-22-hydroxy-5β-furoslane -3β,26-diol-3-O-β-D-g!ucopy ranosyl-U -»4)-β-D-ghicopyranoside (95) The overall reaction scheme is as follows:

Patent-scheme21

Preparation of (93)

To a mixture of compound 10 (1.54 g, 3.12 tnmol) and 89 (2.6 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (30 mL) was added Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at 0 ⁰ C.

The mixture was stirred under room temperature for 15 min, at the end of which time

TLC (petroleum ether-EtOAc, 2:1) indicated that all starting materials were consumed.

The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 89 as a foamy solid (2.96 g, 85%): MALDITOF-MS: Calcd for C ₇₃ H ₈₈ O ₂₂ : 1340.58 [M] ⁺ ; Found 1363.70 [M

+ Na] ⁺ .

Preparation of (94)

The mixture of compound 93 (114 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mL X 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SCi, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 : 1) to give compound 94 as a white solid (74 mg, 65%). MALDITOF-MS: Calcd for C ₇₅ H ₉₀ O ₂₂ : 1342.59 [M] ⁺ ; Found 1365.60 [M + Na] ⁺ .

Preparation of (95)

Compound 94 (70 mg, 0.052 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 IVI NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5.5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:0.5:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 95 as an amorphous solid (38 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.30 (d, 1 H, 7 7.9 Hz, H-I), 5.23 (d, 1 H, 7 7.4 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 104.5, 102.9. MALDITOF-MS: Calcd for C ₃₉ H ₆₆ O ₁₄ : 758.45 [M] ⁺ ; Found 781.31 [M + Na] ⁺ .

Example 22 The preparation of

(25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-furostane -3β,26-diol-3-0-β-D-glucopy ranosyl-( 1 -→4)-β-D-galactopyranoside (98) The overall reaction scheme is as follows:

Patenl-scheme22

Preparation of (96)

To a mixture of 23 (3.1 g, 3.52 mmol) and 89 (3.24 g, 3.2 mmol) in anhyd CH ₂ CU (55 mL) at -20 ⁰ C was added NIS (1.18 g, 5.28 mmol) and Me ₃ SiOTf (63 μL, 0.35 mmol)

under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:2) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 96 as a foamy solid (4.94 g, 85%): MALD1TOF-MS: Calcd for C _1O2 H ₁₁₀ O ₃₀ : 1814.71 [M] ⁺ ; Found 1837.50 [M + Na] ⁺ . Preparation of (97)

The mixture of compound 96 (500 mg, 0.275 mmol) and NaBH ₄ (313 mg, 8.26 mmol) in 2-propanol (24 mL) and CH ₂ Cl ₂ (3 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give aø colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 97 as a white solid (320 mg, 64%); MALD1TOF-MS: Calcd for C^H _{1 I2} O ₃₀ : 1816.72 [M] ⁺ ; Found 1839.50 [M í Na]\ Preparation of (98)

Compound 97 (200 mg, 0.11 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 21 mL), and then 1.0 M NaOMe in MeOH (0.22 mL) was added at 0 ⁰ C. After stirring at room temperature for 4.5 h, TLC (n-BuOH-ElOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H*), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 98 as an amorphous solid (95 mg, 94%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): «55.35 (d, 1 H, J 7.9 Hz, H-I), 5.30 (d, 1 H, J 7.9 Hz ₁ H-I) ₁ 5.20 (d, 1 H, J 7.4 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 104.5, 103.3, 102.9. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ^* ; Found 943.7 [M + Na] ⁺ .

Example 23

The preparation of (25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-furostane-3� �,26-diol-3-0-β-D-glucopy

ranosyl-(l→2)-β-D-galactopyranoside (102) The overall reaction scheme is as follows:

Patent-scheme21

Preparation of (99)

To a mixture of compound 8 (1.38 g, 3.08 mmol) and 89 (2.6 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was added NIS (1.04 g, 4.6 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 99 as a foamy solid (2.94 g, 82%): MALDITOF-MS: Calcd for C _8I H ₈₈ O ₂₀ : 1380.59 [M] ⁺ ; Found 1403.70 [M + Na] '.

Preparation of (100)

To a mixture of compound 10 (685 mg, 1.39 mmol) and 99 (1.6 g, 1.15 mmol) in

anhyd CH ₂ Cl ₂ (15 mL) was added Me ₃ SiOTf (26 μL, 0.14 mmol) under N ₃ atmosphere at - 42 ⁰ C. The mixture was stirred under these conditions for 30 min, at which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, Then he mixture was concentrated with toluene and purified by column chromatography (petroleum ether-EtOAc, 3:1) to give 100 as a white foamy solid (1.5 g, 75%): MALDITOF-MS: Calcd for C _9S Hi ₀₆ O ₂₉ : 1710.68 [M] ⁺ ; Found 1733.75 [M + Na] ⁺ . Preparation of (101) The mixture of compound 100 (150 mg, 0.085 mmol) and NaBIii (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SCi, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 101 as a white solid (102 mg, 68%): MALDITOF-MS: Calcd for C ₉₅ H ₁₀₆ O ₂₉ : 1712.68 [M] ⁺ ; Found 1735.75 [M +Na] ⁺ .

Preparation of (102)

Compound 101 (100 mg, 0.057 ramol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 102 as an amorphous solid (50 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.39 (d, 1 H, 77.9 Hz, H-I), 5.28 (d, 1 H, 77.9 Hz, H-I), 5.19 (d, 1 H, J IA Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 104.0, 103.1, 101.9. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M]'; Found 943.95 [M + Na] ⁺ .

Example 24

The preparation of

(25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-furostane -3β,26-diol-3-0-β-D-glucopy ranosyl-(l -→4)-β-D-glucopyranoside (106) The overall reaction scheme is as follows:

Patent-scheme24

Preparation of (103)

To a mixture of compound 27 (1.57 g, 2.86 mmol) and 89 (2.6 g, 2.6 mraol) in anhyd CH ₂ Cl ₂ (35 mL) was added NlS (643 mg, 2.86 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 103 as a foamy solid (3.09 g, 80%). MALDITOF-MS: Calcd for C ₈₈ H ₉₂ O ₂ ,: 1484.61 [M] ⁺ ; Found 1507.80 [M + Na] ⁺ . Preparation of (104)

To a mixture of compound 10 (834 mg, 1.69 mmol) and 103 (2.1 g, 1.41 mmol) in

anhyd CH ₂ Cl ₂ (18 mL) was added Me ₃ SiOTf (31 μL, 0.17 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 20 min, at which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated to afford 104 as a white foamy solid (2.0 g, 78%). MALDITOF-MS: Calcd for CmH _1I0 O ₃₀ : 1814.71 [M] ⁺ ; Found 1837.8 [M + Na] ⁺ .

Preparation of (105)

The mixture of compound 104 (600 mg, 0.33 mmol) and NaBIi, (312 mg, 8.25 mmol) in 2-propanol (24 mL) and CH ₂ Cl ₂ (3 mL) was stirred at room temperature for about 6.5 h. The reaction mixture was then extracted with CH ₂ CJ ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₁ ), and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 105 as a white solid (313 mg, 67%). MALDITOF-MS: Calcd for Cιo ₂ H» ₂ Oj ₀ : 1816.71 [M] ⁺ ; Found 1839.8 [M + Na] ⁺ . Preparation of (106)

Compound 105 (200 rag, 0.14 mmol) was dissolved in anbyd CH ₃ Cl ₂ - MeOH (1 :2, 27 mL), and then 1.0 M NaOMe in MeOH (0.3 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that lhe reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 106 as an amorphous solid (122 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₃ N): £5.28 (d, 1 H, J 7.9 Hz, H-I), 5.21 (d, I H, / 7.9 Hz, H-I) ₁ 5.20 (d, 1 H, J 7.4 Hz, H-I). ^ϋ C NMR (100 MHz, CD ₅ N): δ 104.1, 103.0, 102.5. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ⁺ ; Found 944.0 [M + Na] ⁺ .

Example 25

The preparation of (25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-fijrostane-3 p,26-diol-3-0-β-D-glucopy

ranosyl-(l→4)-β-D-glucopyranoside (109) The overall reaction scheme is as follows:

Patenl-scheme25 Preparation of (107)

To a mixture of 33 (2.0 g, 1.8 mmol) and 89 (1.66 g, 1.64 mmol) in anhyd CH ₂ Cl ₂ (30 mL) was added NlS (607 mg, 2.7 mmol) and Me ₃ SiOTf (33 μL, 0.18 mmol) under M ₂ atmosphere at O ⁰ C. The mixture was stirred under room temperrature for 30 min, al the end of which time TLC (petroleum ether-EtOAc, 2:1 ) indicated that all starting materials were consumed. The reaction mixture was neutralized wilh TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 107 as a foamy solid (2.88 g, 85%). MALDITOF-MS: Calcd for CmH ₁₁₈ O ₃₀ : 2062.77 [M] ⁺ ; Found 2085.90 [M + Na] ⁺ . Preparation of (108) The mixture of compound 107 (175 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 108 as a

white solid (120 mg, 68%). MALDITOF-MS: Calcd for C ₁₂₂ Ha _O O ₃₀ : 2064.77 [M] ⁺ ; Found 2087.90 [M + Na] ⁺ .

Preparation of (109)

Compound 108 (120 mg, 0.057 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.21 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ¹ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 109 as an amorphous solid (50 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.38 (d, 1 H, 77.4 Hz ₁ H-I), 5.32 (d, 1 H, J 7.5 Hz, H-I), 5.11 (d, 1 H, J 7.9 Hz ₁ H-I). ¹³ C NMR (100

MHz, CD ₅ N): £ 103.5, 103.0, 102.1. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.50 [M] ⁺ ;

Found 943.90 [M + Na] ¹ .

Example 26 The preparation of

(25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-furostane -3p,26-diol-3-0-p-D-glucopy ranosyl-(l →6)-β-D-glucopyranoside (112)

The overall reaction scheme is as follows:

Patent-scheme26

Preparation of (110)

To a mixture of 38 (2.1 g, 2.4 mmol) and 89 (2.02 g, 2.0 mmol) in anhyd CH ₂ Cl ₂ (35 mL) at -20 ⁰ C was added NIS (810 mg, 3.6 mmol) and MejSiOTf (43 μL, 0.24 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 110 as a foamy solid (2.98 g, 82%). MALDITOF-MS: Calcd for C ₁₀₂ Hu ₀ O _3O : 1814.71 [M] ⁺ ; Found 1837.8 [M + Na] ⁺ . Preparation of (111)

The mixture of compound 110 (154 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1.1) to give compound 111 as a white solid (99 mg, 64%). MALDITOF-MS: Calcd for C ₁ Q ₂ Hi _I2 O ₃₀ -. 1816.71 [M] ⁺ ; Found 1839.8 [M + Na] ⁺ .

Preparation of (112) Compound 111 (80 mg, 0.056 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2,

18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 111 as an amorphous solid (50 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ5Al (d, 1 H ₁ / 7.1 Hz, H-I), 5.33 (d, 1 H, J 1.5 Hz ₁ H-I), 5.12 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): 5 103.7, 103.0, 102.5. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₉ : 920.5 [M] ⁺ ; Found 943.8 [M + Na] ⁺ .

Example 27

The preparation of

(25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-fuτostan e-3β,26-dJol-3-0-α-L- rhamnopyranosyl-(l→2)-β-D-glucopyranosicie (115) The overall reaction scheme is as follows:

Patent-scheme27

Preparation of (113) To a mixture of compound 42 (1.5 g, 2.4 mmol) and 103 (3.27 g, 2.2 mmol) in anhyd CH ₂ Cl ₂ (50 raL) at -20 ⁰ C was added TMSOTf (44 μL, 0.24 mmol). The mixture was stirred at these conditions for 40 min, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 113 (3.68 g, 86%). MALDITOF-MS: Calcd for C ₁₁₅ H ₁ MO _2B : 1942.75 [M] ⁺ ; Found 1965.60 [M + Na] ⁺ . Preparation of (114)

The mixture of compound 113 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-proρanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 114 as a white solid (115 mg, 70%). MALDITOF-MS: Calcd for C ₁₁₅ Hi _I6 O ₂₈ : 1944.75 [M] ⁺ ; Found 1967.60 [M + Na] ⁺ . Preparation of (115)

Compound 114 (100 mg, 0.051 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 °C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 115 as an amorphous solid (44 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): <S5.53 (d, ] H, J 2.5 Hz, H-I), 5.30 (d, 1 H, J 7.1 Hz, H-I), 5.20 (d, 1 H, Jl 2 Hz ₁ H-I). ¹³ C NMR (100 MHz, CD ₅ N): «5105.5, 103.1, 102.2. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 947.80 [M + Na] ⁺ .

Example 28

The preparation of (25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-rurostane-3� �,26- diol-3-O-α-L- rhamnopyτanosyl -(l→4)-β-D-glucopyτanoside (118) The overall reaction scheme is as follows:

Patent-scheme28

Preparation of (116)

To a mixture of 46 (2.1 g, 2.11 mmol) and 89 (1.94 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (45 mL) at -20 ⁰ C was added NIS (712 mg, 3.2 mmol) and Me ₃ SiOTf (38 μL, 0.211 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30

rain, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 116 as a foamy solid (3.17 g, 85%). MALDITOF-MS: Calcd for C ₁₁₅ HmO ₂₈ : 1942.75 [M] ⁺ ; Found 1965.60 [M + Na]'. Preparation of (117)

The mixture of compound 116 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cb (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CHaCl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1: 1) to give compound 117 as a white solid (115 mg, 70%). MALDITOF-MS: Calcd for C ₁₁₅ H ₁₁₆ O ₂₈ : 1944.75 [M] ⁺ ; Found 1967.60 [M + Na] ⁺ . Preparation of (118)

Compound 117 (100 mg, 0.051 mmol) was dissolved in anhyd CH ₂ Cl ₃ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 118 as an amorphous solid (44 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.53 (d, 1 H, ./ 2.6 Hz, H-I), 5.21 (d, 1 H, 77.5 Hz ₁ H-I), 5.19 (d, 1 H, /7.4 Hz, H-I). ¹³ C NMR (100 MHz ₁ CD ₅ N): 5105.5, 103.7, 102.1. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 947.80 [M + Na] ⁺ .

Example 29

The preparation of (25S)-26-O-β-D-galactopyranosyl-22-hydroxy-5β-furostane-3� �,26- diol-3-O-α-L- rhamnopyranosyl -(l→6)-β-D-galactopyranoside (121) The overall reaction scheme is as follows:

Patent-scheme29

Preparation of (119)

To a mixture of Sl (2.1 g, 2.11 mxnol) and 89 (1.94 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (40 mL) at -20 ⁰ C was added NIS (712 mg, 3.2 mmol) and Me ₃ SiOTf (38 μL, 0.211 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 119 as a foamy solid (3.17 g, 85%). MALDITOF-MS: Calcd for C _m Hι _M 0 _2a : 1942.75 [M] ⁺ ; Found 1965.60 [M + Na] ⁺ . Preparation of (120)

The mixture of compound 119 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 120 as a white solid (115 mg, 68%). MALDITOF-MS: Calcd for Ci ₁₅ H ₁₁₄ O ₂₈ : 1944.75 [M] ⁺ ; Found 1967.60 [M + Na] ⁺ . Preparation of (121)

Compound 120 (100 mg, 0.057 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, I S mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 121 as an amorphous solid (44 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.55 (d, 1 H, /2.7 Hz, H-I), 5.30 (d, 1 H, J 7.5 Hz, H-I), 5.16 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.9, 103.4, 102.5. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 927.80 [M + Na] ⁺ .

Example 30

The preparation of (25S)-26-O-β-D-galactopyranosyl-22-hydroxy-5β-furostane-3� �,26- diol-3-O-[α-L- rhamnopyranosyl-(l →4)]-[α-L-rhamnopyranosyl-( 1 -→2)]-β-D- glucopyranoside (125) The overall reaction scheme is as follows:

Patent-scheme30

Preparation of (122)

To a mixture of 55 (996 mg, 2.30 mmol) and 89 (1.94 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -40 ⁰ C was added NIS (517 mg, 2.30 mmol) and Me ₃ SiOTf (42 μL, 0.23 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, lhen concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 122 as a foamy solid (2.12 g, 80%). MALDITOF-MS: Calcd for C _8I H ₈₈ O ₂₀ : 1380.59 [M] ⁺ ; Found 1403.70 [M + Na] ⁺ .

Preparation of (123)

To a mixture of 122 (2.0 g, 1.45 mmol) and 42 (2.16 g, 3.48 mmol) in anliyd CH ₂ Cl ₂ (30 mL) at -20 ⁰ C was added Me ₃ SiOTf (62 μL, 0.34 mmol) under N ₂ atmosphere at - 20

⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 123 as a foamy solid (2.83 g, 85%). MALDITOF-MS: Calcd for C ₁₃₅ H ₁₃₂ O ₃₄ : 2296.86 [M] ⁺ ; Found 2319.90 [M + Na] ⁺ .

Preparation of (124)

The mixture of compound 123 (195 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 raL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CHiCU (100 mLX 2), the combined organic layer was washed with water (100 mL X 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vaαium to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 : 1) to give compound 124 as a white solid (121 mg, 68%). MALDITOF-MS: Calcd for C ₁₃₃ H ₁₃₁₁ O ₃₄ : 2298.86 [M]' ; Found 2321.90 [M + Na] ⁺ . Preparation of (125)

Compound 124 (120 mg, 0.052 mmol) was dissolved in anhyd CH ₂ CIi - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :1) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (If*), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 125 as an amorphous solid (53 mg, 97%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.53 (d, 1 H, J 2.5 Hz, H-I), 5.50 (d, 1 H, J 2.6 Hz, H-I), 5.22 (d, 1 H, J 7.3 Hz, H-I), 5.17 (d, 1 H, J 7.2 Hz ₁ H-I). ¹³ C NMR (100 MHz ₁ CD ₅ N): δ 105.5, 104.8, 103.0, 102.5. MALDITOF-MS: Calcd for C ₅₁ H ₈₆ O ₂₂ : 1050.56 [M] ⁺ ; Found 1073.80 [M + Na] ¹ .

Example 31

The preparation of (25S)-26-0-β-D-ga]actopyranosyl-22-hydroxy-5p-furostane-3β ,26-diol-3-0-[β-D-

glucopyranosyKl→4)]-[α-L- rhaπ ⁱ nopyranosyl-(l->2)]-β-D-glucopyranosidc (128) The overall reaction scheme is as follows:

Patent-scheme31

Preparation of (126)

To a mixture of compound 122 (2.5 g, 1.81 mmol) and 42 (1.35 g, 2.17 πunol) in anhyd CH ₂ Cl ₂ (50 mL) at -40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at these conditions for 40 rain, then the mixture was added 10 (1.07 g, 2,17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at O ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography

(petroleum ether-EtOAc, 2:1) of the residue gave 126 as a foamy solid (3.10 g, 79%). MALDITOF-MS: Calcd for Cj ₂₂ H _12B O ₃₆ : 2168.82 [M] ⁺ ; Found 2192.0 [M + Na] ⁺ .

Preparation of (127)

The mixture of compound 126 (185 mg, 0.085 mmol) and NaBH, (96 mg, 2.5 mmol) in 2-proρanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1: 1} to give compound 127 as a white solid (118 mg, 64%). MALD1TOF-MS: Calcd for CI ₂₂ HI ₃ OO ₃₆ : 2170.82 [M] ⁺ ; Found 2194.0 [M + Na] ⁺ . Preparation of (128)

Compound 127 (100 mg, 0.046 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) radicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 128 as an amorphous solid (47 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.53 (d, 1 H, /2.5 Hz, H-I ), 5.30 (d, 1 H, J 6.9 Hz, H-I), 5.20 (d, 1 H, J 7.5 Hz, H-I ), 5.09 (d, 1 H ₁ J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.8, 103.0, 102.1. MALDTTOF-MS: Calcd for C ₅₁ H ₈₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.72 [M + Na] ⁺

Example 32

The preparation of (25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-rurostane-3� �,26-diol-3-0-[α-L- rhamnopyranosyI-(l→4)]-[β-D-glucopyranosyl-(l→2)]-β-D- glucopyranoside (131) The overall reaction scheme is as follows:

Patent-scheme32

Preparation of (129)

To a mixture of compound 122 (2.5 g, 1.81 mmol) and 5 (1.61 g, 2.17 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at - 40 ⁰ C was added TMSOTf (40 μh, 0.22 mmol). The mixture was stirred al these conditions for 40 min, then the mixture was added 42 (1.35 g, 2.17 mmol) and TMSOTf (40 μL, 0.22 mmol),under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc,

1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 129 as a foamy solid (3.46 g, 79%).

MALD1TOF-MS: Calcd for C ₄₂ H ₁₃₆ O ₃₆ : 2416.88 [M] ⁺ ; Found 2439.75 [M + Na] ⁺ .

Preparation of (130)

The mixture of compound 129 (206 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by

column chromatography (petroleum ether/ethyl acetate, 1: 1) to give compound 130 as a white solid (123 mg, 60%). MALDITOF-MS: Calcd for C ₁₄₂ Hi ₃₈ O ₃₆ : 2418.88 [M] ⁺ ; Found 2441.75 [M + Na] ⁺ . Preparation of (131) Compound 130 (120 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2,

18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-ge] P ₂ column to afford 131 as an amoφhous solid (51 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.56 (d, 1 H, 72.5 Hz, H-I), 5.22 (d, 1 H, / 6.9 Hz, H-I) ₁ 5.19 (d, 1 H, J 7.5 Hz, H-I), 5.10 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.1, 103.0, 102.6. MALDITOF-MS: Calcd for C _5I H ₆₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.72 [M + Na] ⁺ .

Example 33

The preparation of

(25S)-26-0-β-D-galactopyranosyl-22-hydroxy-5β-furostane -3β,26-dioI-3-0-[β-D-glucop yranosyl-(l→4)]-[α-L- rhamnopyranosyl -(l→2)J-β-D-galactopyranoside (134) The overall reaction scheme is as follows:

Patent-scheme33

Preparation of (132)

To a mixture of compound 99 (2.5 g, 1.81 mraol) and 42 (1.35 g, 2.17 raraol) in anhyd CH ₂ Cl ₂ (50 mL) at - 40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at these conditions for 40 min, then the mixture was added S (1.61 g, 2.17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-ElOAc,

1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 132 as a foamy solid (3.46 g, 79%).

MALDITOF-MS: Calcd for CH ₂ H ₁₃₆ O ₃₆ : 2416.88 [M] ⁺ ; Found 2439.75 [M + Na] ⁺ .

Preparation of (133)

The mixture of compound 132 (206 mg, 0.085 mmol) and NaBIi, (96 mg, 2.5 ramol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum etber/ethyl acetate, 1 :1) to give compound 133 as a

white solid (123 mg, 60%). M ALDITOF-MS: Calcd for C ₁₄₂ H ₁₃₈ O ₃₆ : 2418.88 [M]"; Found 2441.75 [M + Na] ⁺ .

Preparation of (134)

Compound 133 (120 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then ^" filtered aud cuuccntratedrT-he rcaidυc-wos purified-by itig-gni P ₁ rol^mn tn afford 134 as an amorphous solid (49 mg, 93%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.49 (d, 1 H, J 2.5 Hz, H-I), 5.30 (d, 1 H, J 6.9 Hz, H-I), 5.24 (d, 1 H, J 7.5 Hz, H-I), 5.12 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.5, 103.1, 102.4. MALD1TOF-MS: Calcd for C ₅₁ H ₈₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.72 [M + Na] ⁺ .

Example 34

The preparation of

(25S)-26-0-β-D-galactopyranosyl-22-nydroxy-5β-rurostane -3β,26-diol-3-0-[α-L- rhamnopyranosyl-(l→4)]-[β-D-glucopyranosyl-(l→2)]-β-D- galactopyranoside (137) The overall reaction scheme is as follows:

Patent-scheme34

Preparation of (135)

To a mixture of compound 99 (2.5 g, 1.81 rnmol) and S (1.61 g, 2.17 mmol) in anhyd

CI-I ₂ Cl ₂ (50 raL) at - 40 ⁰ C was added TMSOTf (40 μL, 0.22 mmol). The mixture was stirred at lhese conditions for 40 min, then the mixture was added 42 (1.35 g, 2.17 mmol) and TMSOTf (40 μL, 0.22 mmol).under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc,

1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 135 as a foamy solid (3.46 g, 79%). MALDγγOF-MS: Calcd for C ₁₄₂ H ₁₃₆ O ₃₆ : 2416.88 [M] ⁺ ; Found 2439.75 [M + Na] ⁺ .

Preparation of (136)

The mixture of compound 135 (206 mg, 0.085 mmol) and NaBIi ₁ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 9 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mL X 2), the combined organic layer was washed with water (100 mL X 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 136 as a white solid (123 mg, 60%). MALDITOF-MS: Calcd for C _NJ H ₁₃₈ O ₃₆ : 2418.88 [M] ⁺ ; Found 2441.75 [M + Na] ⁺ . Preparation of (137)

Compound 136 (120 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (H-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 137 as an amorphous solid (49 mg, 93%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.55 (d, 1 H, J 2.5 Hz, H-I), 5.24 (d, 1 H, J 6.9 Hz ₁ H-I), 5.20 (d, 1 H, / 7.5 Hz, H-I), 5.08 (d, 1 H, J 12 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.9, 103.2, 103.1, 102.5. MALDγTOF-MS: Calcd for C ₅₁ H ₈₆ O ₂₃ : 1066.56 [M] ^1' ; Found 1089.72 [M+ Na] ⁺ .

Example 35

The preparation of

(25S)-26-0-β-D.galactopyranosyl-22-hydroxy-5β-njrostane-3p ,26-diol-3-0-β-D-glucopy ranosyl-(l→4)-β-D-glucopyranosy ^] -(l→4)-β-D-galactopyranσside {140) The overall reaction scheme is as follows:

Patent-scheme35 Preparation of (138)

To a mixture of 73 (2.0 g, 1.7 mmol) and 89 (1.57 g, 1.55 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added NTS (562 rag, 2.5 mmol) and Me ₃ SiOTf (Sl μL, 0.17 mmol) under Ni atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 138 as a foamy solid (2.71 g, 83%). M ALDITOF-MS: Calcd for C _{J M} H ₁₂₆ O ₃₈ : 2102.79 [M] ⁺ ; Found 2125.90 [M + Na]' . Preparation of (139) The mixture of compound 138 (179 mg, 0.085 mmol) and NaBR, (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum etber/ethyl acetate, 1: 1) to give compound 139 as a white solid (116 mg, 67%). MALDITOF-MS: Calcd for C _M H ₁₂₈ O ₃₈ : 2104.79 [M] ⁺ ; Found 2127.90 [M + Na] ⁺ . Preparation of (140)

Compound 139 (100 mg, 0.047 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 140 as an amorphous solid (49 rag, 96%): Selected ¹ H NMR (400 MHz ₁ C ₆ D ₅ N): δ 5.35 (d, 1 H, 77.5 Hz ₁ H-I), 5.30 (d, 1 H, 76.9 Hz ₁ H-I), 5.27 (d, 1 H, J 7.5 Hz, H-I), 5.05 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz ₁ CD ₃ N): δ 103.5, 103.1, 103.0, 102.5. MALDITOF-MS: Calcd for C ₅₁ H ₈₆ O ₂₄ : 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺ .

Example 36

The preparation of (25S)-26-O-β-D-galactopyranosyl-22-hydroxy-5β-furostane-3� �.26-diol-3-O-β-D-glucopy ranosyl-(l→4)-β-D-glucopyranosyl-(l→2)-β-D-galactopyra noside (143) The overall reaction scheme is as follows:

Patent-scheme36

Preparation of (141)

To a mixture of compound 72 (2.5 g, 3.20 mmol) and 99 (4.02 g, 2.91 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -40 ⁰ C was added TMSOTf (58 μL, 0.32 mmol). The mixture was stirred at these conditions for 1 h, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 141 (4.54 g, 78%).

MALDITOF-MS: Calcd for C ₁₀₇ H ₁₂₂ O ₃₇ : \ 998.77 [M]'; Found 2021.90 [M + Na] ⁺ .

Preparation of (142) The mixture of compound 141 (170 mg, 0.085 mmol) and NaBI-I ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CHjCl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO^, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 142 as a white solid (116 mg, 68%). MALDITOF-MS: Calcd for C ₁₀₇ H ₁₂₄ O ₃₇ : 2000.77 [M] ⁺ ; Found 2023.90 [M + Na] ⁺ .

Preparation of (143)

Compound 142 (100 mg, 0.05 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 143 as an amorphous solid (51 mg, 94%): Selected ¹ H NMR (400 MHz ₁ C ₆ D ₅ N): £5.37 (d, 1 H, 76.9 Hz, H-I), 5.28 (d, 1 H, J 7.6 Hz, H-I), 5.19 (d, 1 H, / 7.5 Hz, H-I), 5.04 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 103.1 , 102.8, 102.5, 102.1. MALDITOF-MS: Calcd for C ₅₁ H ₈₅ O ₂₄ : 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺ .

Example 37 The preparation of

(25S)-26-0-P-D-galactopyranosyl-22-hydroxy-5β-furostane- 3β,26-diol-3-0-β-D-glucopy ranosy!-(l-»4)-β-D-glucopyranosyl-(l→4)-β-D-glucopyrano side (146) The overall reaction scheme is as follows:

Patent-scheme37

Preparation of (144)

To a mixture of 80 (2.5 g, 2.16 mmol) and 89 (1.98 g, 1.96 mmol) in anhyd CH ₂ Cl ₂ (50 mL) at -20 ⁰ C was added NIS (729 mg, 3.24 mmol) and Me ₃ SiOTf (40 μL, 0.22 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 1 : 1) of the residue gave 144 as a foamy solid (3.51 g, 85%). M ALDlTOF-MS: Calcd for C ₁₁₄ H ₁₂₆ O ₃₈ : 2102.79 [M] ⁺ ; Found 2125.90 [M + Na] ⁺ . Preparation of (145) The mixture of compound 144 (179 mg, 0.085 mmol) and NaBI-L, (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SCi, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1 ) to give compound 145 as a white solid (116 mg, 67%). MALDITOF-MS: Calcd for C ₁₁₄ Hn ₈ O ₃ Ii: 2104.79 [M] ⁺ ; Found 2127.90 [M + Na] ⁺ . Preparation of (146) Compound 145 (100 mg, 0.047 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 146 as an amorphous solid (49 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.29 (d, 1 H, / 7.1 Hz, H-I), 5.23 (d, 1 H, 76.9 Hz, H-I), 5.20 (d, I H, / 7.5 Hz, H-I), 5.04 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 103.6, 103.4, 102.8, 101.6. MALDITOF-MS: Calcd for C _5I H ₈₅ O ₂₄ : 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺ .

Example 38

The preparation of

(25S)-26-O-β-D-galaclopyranosyl-22-hydroxy-5β-ftιrosla ne-3p,26-diol-3-O-β-D-glucopy ranosyl-(l-→.4)-β-D-gtucopyranosyl-(l→2)-β-D-glucopyra Dθside (149) The overall reaction scheme is as follows:

Pateπt-scbeme38 Preparation of (147)

To a mixture of compound 103 (5.8 g, 3.9 ramol) and 72 (3.6 g, 4.6 ramol) in anhyd CH ₂ Cl ₂ (55 mL) at -20 ⁰ C was added TMSOTf (83 μL, 0.46 mrαol). The mixture was stirred at these conditions for 30 miπ, then neutralized with TEA, and concentrated. The residue was purified by column chromatography to give a foamy solid 147 (6.97 g, 85%). MALDITOF-MS: Calcd for C _{1 H} H ₁₂₆ O ₃₈ : 2102.79 [M] ⁺ ; Found 2125.90 [M + Na] ⁺ . Preparation of (148)

The mixture of compound 147 (179 mg, 0.085 mmol) and NaBE ₁ (96 mg, 2.5 mmol) ki 2-propaπol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h.

The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO,), and the

solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 148 as a white solid (116 mg, 67%). MALDITOF-MS: Calcd for C ₁₁₄ H ₁₂₈ Oj ₈ : 2104.79 [M] ⁺ ; Found 2127.90 [M + Na] ⁺ . Preparation of (149)

Compound 148 (100 mg, 0.047 mmol) was dissolved in anhyd CH ₃ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added al 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 149 as an amorphous solid (50 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ M): «55.27 (d, 1 H, / 7.5 Hz, H-I), 5.30 (d, 1 H, / 7.9 Hz, H-I), 5.22 (d, 1 H, / 7.5 Hz, H-I), 5.05 (d, 1 H, / 7.3 Hz, H-I). ¹¹ C NMR (100 MHz, CD ₅ N): δ 103.5, 103.1 , 102.3, 101.6. MALDITOF-MS: Calcd for C ₃₁ H ₈₆ O ₂₄ : 1082.55 [M] ⁺ ; Found 1105.70 [M + Na] ⁺

Example 39

The preparation of (25S)-26-0-α-L-rhamnopyranosyl-22-hydroxy-5β-rurostane-3β ,26-diol-3-0-β-D- galactopyranoside (154)

Pateπt-scheme39

Preparation of (151)

To a mixture of compounds 4 (2.25 g, 4.1 mmol) and 42 (2.98 g, 4.8 mmol, commercially available) in anhyd CH ₂ Cl ₂ (36 mL) was added Me ₃ SiOTf (86 μL, 0.47 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for

40 min, at the end of which time TLC (petroleum elher-EtOAc, 4:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with triethylamine (TEA), then concentrated. Column chromatography (petroleum ether-EtOAc, 6:1) of the residue gave 150 as a foamy solid (3.29 g, 80%).

To a solution of compound 150 (3.2 g, 3.2 mmol) in dry CH ₂ CI ₂ (40 mL) was added BF ₃ Et ₂ O (1.0 mL, 7.3 mmol), and the mixture was stirred at room temperature for 4 h, and TLC (petroleum ether-EtOAc, 1:1) indicated that the reaction was complete. The mixture was diluted with CH ₂ CI ₂ , washed with said aq NaHCO ₃ and then satd aq NaCl. The organic layer was combined, dried, and concentrated. Purification by column chromatography (petroleum ether-EtOAc, 3:1) gave 151 as a white foamy solid (2.71 g, 95%): MALDITOF-MS: Calcd for C ₅₄ H ₄₆ O ₁₁ : 890.46 [UY; Found 913.60 [M + Na] ⁺ Preparation of (152)

To a mixture of compound 87 (2.30 g, 3.10 mmol) and 151 (2.32 g, 2.6 mmol) in anhyd CHjCl ₂ (50 mL) was adde Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under r.t. for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 2:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 152 as a foamy solid (3.44 g, 90%): MALDITOF-MS: Calcd for C ₈₈ H ₉₂ O ₂₀ : 1468.62 [M] ⁺ ; Found 1491.75 [M + Na] ⁺ . Preparation of (153)

The mixture of compound 152 (558 mg, 0.38 mmol) and NaBH ₄ (357 rag, 9.4 mmol) in 2-propanol (16 mL) and CH ₂ Cl ₂ (2 mL) was stirred at room temperature for about 7.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic

layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 153 as a white solid (363 mg, 65%): MALDITOF-MS: Calcd for C ₈₈ H ₉₄ O ₂₀ : 1470.62 [M] ⁺ ; Found 1493.75 [M + Na] ⁺ .

Preparation of (154)

Compound 153 (190 mg, 0.13 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 24 mL), and then 1.0 M NaOMe in MeOH (0.25 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:0.5:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (rOi ⁰ ^ then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 154 as an amorphous solid (92 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₃ N): £ 5.53 (d, 1 H, J 2.5 Hz, H-I), 5.30 (d, 1 H, /6.9 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.1. MALDITOF-MS: Calcd for C ₃₉ H ₆₆ O ₁₃ : 742.45 [M] ⁺ ; Found 765.50 [M + Na] ⁺ .

Example 40

The preparation of

(25S)-26-O-a-L-rhamnopyranosyl-22-hydroxy-5p-n.rostane-3p ,26-diol-3-O-P-D-glucopy ranosyl-(l →2)-β-D-galactopyranoside (158) The overall reaction scheme is as follows:

Patent-scheme40

Preparation of (155)

To a mixture of compound 8 (1.38 g, 3.08 rnmol) and 151 (2.3 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was added NIS (692 mg, 3.08 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 155 as a foamy solid (2.69 g, 82%): MALDITOF-MS: Calcd for C ₇₁₁ H ₈₄ O ₁₈ : 1260.57 [M] ⁺ ; Found 1283.70 [M + Na] ⁺ .

Preparation of (156)

To a mixture of compound 10 (685 mg, 1 ,39 mmol) and 155 (1.45 g, 1.15 mmol) in anliyd CH ₃ Cl ₂ (15 mL) was added Me ₃ SiOTf (26 μL, 0.14 mmol) under N ₂ atmosphere at - 42 ⁰ C. The mixture was stirred under these conditions for 30 min, at which time TLC

(petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, Then he mixture was concentrated with toluene and purified by column chromatography (petroleum ether-EtOAc, 3:1) to give 156 as a white foamy solid (1.37 g, 75%); MALDITOF-MS: Calcd for C ₈₈ H ₁₀₂ O ₂₇ : 1590.66 [M] ⁺ ; Found 1613.75 [M + Na] ⁺ . Preparation of (157)

The mixture of compound 156 (135 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 ramol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ CIa (300 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 157 as a white solid (88 mg, 65%): MALDITOF-MS: Calcd for Cg ₈ Hu _M O ₂₇ : 1592.66 [M] ⁺ ; Found 1615.75 [M + Na] ⁺ . Preparation of (158)

Compound 157 (80 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 158 as an amorphous solid (43 mg, 95%); Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.53 (d, 1 H, 72.5 Hz, H-I), 5.25 (d, 1 H, 77.5 Hz, H-I) ₁ 5.09 (d, I H ₁ 77.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): 5105.5, 103.0, 102.1. MALDITOF-MS: Calcd for C _4S H _7fi O, _g : 904.50 [M] ⁺ ; Found 927.75 [M + Na] ⁺ .

Example 41 The preparation of

(25S)-26-0-α-L-rliamnopyranosyl-22-hydroxy-5p-furostane- 3p,26-diol-3-0-[α-L- rhamnopyranosyl-(l-→4)]-[α-L-rhamnopyranosyl-(l-→2)]-β -D-glucopyranoside (162)

The overall reaction scheme is as follows:

Patent-scheme 41

Preparation of (159)

To a mixture of 55 (996 mg, 2.30 mmol) and 151 (1.71 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -40 ⁰ C was added MS (517 mg, 2.30 mmol) and Me ₃ SiOTf (42 μL, 0.23 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 159 as a foamy solid (1.94 g, 80%). M ALDITOF-MS: Calcd for C ₇₄ H ₈₄ O ₁₈ : 1260.57 [M] ⁺ ; Found 1283.70 [M + Na] ⁺ .

Preparation of (160)

To a mixture of 159 (1.83 g, 1.45 πunol) and 42 (2.16 g, 3.48 mmol) in anhyd CH ₂ Cl ₂ (30 mL) at -20 ⁰ C was added Me ₃ SiOTf (62 μL, 0.34 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 160 as a foamy solid (2.68 g, 85%). MALDITOF-MS: Calcd for C ₁₃₈ H ₁₂₈ O ₃₂ : 2176.84 [M] ⁺ ; Found 2199.90 [M + Na] ⁺ .

Preparation of (161) The mixture of compound 160 (185 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ CIj (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ CIj (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 161 as a white solid (124 mg, 67%). MALDITOF-MS: Calcd for C ₁₂₈ H ₁₃₀ O ₃₂ : 2178.84 [M] ⁺ ; Found 2201.90 [M + Na] ⁺ . Preparation of (162) Compound 161 (120 mg, 0.055 mraol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :1) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ). and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 125 as an amorphous solid (55 mg, 97%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.53 (d, 1 H, / 2.5 Hz, H-I), 5.50 (d, 1 H, J 2.6 Hz, H-I) ₁ 5.41 (d, 1 H, 72.6 Hz, H-I), 5.09 (d, 1 H, J 7.2 Hz, PI-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 105.3, 104.8, 102.1. MALDITOF-MS: Calcd for C ₅₁ H ₈₆ O _2I : 1034.57 [M] ⁺ ; Found 1057.70 [M + Na] ⁺ .

Example 42

The preparation of

(25S)-26-0-α-L-rhamnopyranosyl-22-hydroxy-5P-ftιrostane -3β,26-diol-3-0-P-D-glucopy ranosyl-(l->4)-p-D-gIucopyranosyl-(I→4)-β-D-galactopyr anoside (16S)

The overall reaction scheme is as follows:

Patent-scheme 42

Preparation of (163)

To a mixture of 73 (2.0 g, 1.7 ramol) and 151 (1.38 g, 1.55 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -20 ⁰ C was added NIS (562 mg, 2.5 mmol) and Me ₃ SiOTf (31 μL, 0.17 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 163 as a foamy solid (2.55 g, 83%). MALDITOF-MS: Calcd for C _{1 W} H ₁₂₂ O ₃₆ : 1982.77 [M] ⁺ ; Found 2005.90 [M + Na]'. Preparation of (164)

The mixture of compound 163 (168 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2,5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mL X 2), the combined organic

layer was washed with water (100 mLX 3) and dried over anhydrous NaISO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 164 as a white solid (113 mg, 67%). MALD1TOF-MS; Calcd for Ci ₁₀₇ H ₁₂₄ O ₃₆ : 1984.77 [M] ^H ; Found 2007.90 [M + Na] ⁺ . Preparation of (165)

Compound 164 (110 mg, 0.055 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 140 as an amorphous solid (56 mg, 96%): Selected ¹ H NMR (400 MtIz, C ₆ D ₃ N): «55.53 (d, 1 H, J 2.5 Hz, H-I), 5.25 (d, 1 H ₁ / 6.9 Hz, H-I), 5.21 (d, 1 H, J 7.5 Hz, H-I), 5.04 (d, 1 H, J 12 Hz, H-I ). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.1, 103.0, 102.6. MALDITOF-MS: Calcd for C ₅ )H ₈₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.70 [M + Na] ⁺ .

Example 43

The preparation of

(25S)-26-O-α-L-fucopyranosyl-22-hydroxy-5β-furostane-3� �,26-diol-3-O-β-D- galactopyranoside (171)

The overall reaction scheme is as follows:

Patent-scheme 43

Preparation of (168)

To a mixture of compounds 4 (2.25 g, 4.1 ramol) and 166 (2.98 g, 4.8 mmσl, commercially available) in anhyd CH ₂ Cl ₂ (36 mL) was added Me ₃ SiOTf (86 μL, 0.47 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for

40 min, at the end of which time TLC (petroleum ether-EtOAc, 4:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with triethylamine (TEA), then concentrated. Column chromatography (petroleum ether-EtOAc, 6:1) of the residue gave 167 as a foamy solid (3.29 g, 80%). To a solution of compound 167 (3.2 g, 3.2 mmol) in dry CH ₂ Cl ₂ (40 mL) was added

BF ₃ -Et ₂ O (1.0 mL, 7.3 mraol), and the mixture was stirred at room temperature for 4 h, and TLC (petroleum ether-EtOAc, 1: 1) indicated that the reaction was complete. The mixture was diluted with CH ₂ Cl ₂ , washed with satd aq NaHCOj and then satd aq NaCl.

The organic layer was combined, dried, and concentrated. Purification by column chromatography (petroleum ether-EtOAc, 3:1 ) gave 168 as a white foamy solid (2.71 g,

95%): MALDITOF-MS: Calcd for C ₅₄ H ₆₆ O ₁₁ : 890.46 [M] ⁺ ; Found 913.60 [M + Na] ⁺

Preparation of (169)

To a mixture of compound 87 (2.30 g, 3.10 mmol) and 168 (2.32 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was adde Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at 0 ⁰ C. The mixture was stirred under r.t. for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 2: 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 169 as a foamy solid (3.44 g, 90%): MALDITOF-MS: Calcd for C _8B H ₉₂ O ₂₀ : 1468.62 [M] ⁺ ; Found 1491.75 [M + Na] ⁺ . Preparation of (170)

The mixture of compound 169 (558 mg, 0.38 mmol) and NaBH ₄ (357 mg, 9.4 mmol) in 2-propanol (16 mL) and CH ₂ Cl ₂ (2 mL) was stirred at room temperature for about 7.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the

solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 170 as a white solid (363 mg, 65%): MALDITOF-MS: Calcd RJr C ₈₈ H ₉₄ O ₂₀ : 1470.62 [M] ¹ ; Found 1493.75 [M + Na] ⁺ . Preparation of (171)

Compound 170 (190 mg, 0.13 mmol) was dissolved in anhyd CHiCl ₂ - MeOH (1 :2, 24 mL), and then 1.0 M NaOMe in MeOH (0.25 mL) was added at 0 ^G C. Aλer stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-HjO, 2:0.5:0.5) indicated lhat lhe reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 171 as an amorphous solid (92 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): «55.51 (d, 1 H, /2.5 Hz, H-I), 5.21 (d, 1 H, J 6.9 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): 5105.5, 103.0. MALDγTOF-MS: Calcd for C ₃₉ H ₆₆ Oi ₃ : 742.45 [M] ⁺ ; Found 765.50 [M + Na]".

Example 44

The preparation of

(25S)-26-0-α-L-fυcopyranosyl-22-hydroxy-5β-furostane-3 β,26-diol-3-0-β-D-glucopyran osyl-(l→2)-β-D-gaIactopyranoside (175)

The overall reaction scheme is as follows:

Patent-scheme 44

Preparation of (172)

To a mixture of compound 8 (1.38 g, 3,08 mmol) and 168 (2.3 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was added NTS (692 rag, 3.08 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 172 as a foamy solid (2.69 g, 82%): MALDITOF-MS: Calcd for C ₇₄ H ₈₄ O ₁₈ : 1260.57 [M]'; Found 1283.70 [M + Na] ⁺ . Preparation of (173)

To a mixture of compound 10 (685 mg, 1.39 mmol) and 172 (1.45 g, 1.15 mmol) in anhyd CH ₂ Cl ₂ (15 mL) was added Me ₃ SiOTf (26 μL, 0.14 mmol) under N ₂ atmosphere at - 42 ⁰ C. The mixture was stirred under these conditions for 30 min, at which time TLC

(petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, Then he mixture was concentrated with toluene and purified by column chromatography (petroleum ether-EtOAc, 3:1 ) to give 173 as a white foamy solid (1.37 g, 75%): MALDITOF-MS: Calcd for C ₈₈ Hi ₀₂ O ₂₇ : 1590.66 [M] ⁺ ; Found 1613.75 [M + Na]' . Preparation of (174)

The mixture of compound 173 (135 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ CI ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ CI ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 174 as a white solid (88 mg, 65%): MALDITOF-MS: Calcd for C ₈₈ Hi ₀₄ O ₂₇ : 1592.66 [M] ⁺ ; Found 1615.75 [M H- Na] ⁺ . Preparation of (175)

Compound 174 (80 mg, 0.050 mmol) was dissolved in anhyd CH ₂ CIi - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (H-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated thai the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel PT column to afford 175 as an amorphous solid (43 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ DjN): «55.53 (d, 1 H, J 2.5 Hz, H-I), 5.23 (d, 1 H ₁ J 7.5 Hz, H-I ), 5.11 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): S 105.5, 103.0, 102.4. MALDITOF-MS: Calcd for C ₄₅ H ₇₆ O ₁₈ : 904.50 [M] ⁺ ; Found 927.75 [M + Na]\

Example 45 The preparation of

(25S)-26-0-α-L-fucopyranosyl-22-hydroxy-5β-furostane-3� �,26-diol-3-0-[α-L- rhamnopyranosyl-(l→4)]-[α-L-rhamnopyranosyl-(l→2)]-β-D -glucopyranoside (179)

The overall reaction scheme is as follows:

Patenl-scheme45

Preparation of (176)

To a mixture of 55 (996 mg, 2.30 mmol) and 168 (1.71 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -40 ⁰ C was added NIS (517 mg, 2.30 mmol) and Me ₃ SiOTf (42 μL, 0.23 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 176 as a foamy solid (1.94 g, 80%). MALDITOF-MS: Calcd for C ₇₄ H ₈₄ O ₁₈ : 1260.57 [M] ⁺ ; Found 1283.70 [M + Na^.

Preparation of (177)

To a mixture of 176 (1.83 g, 1.45 mmol) and 42 (2.16 g, 3,48 mmol) in aαhyd CH ₂ Cl ₂ (30 mL) at -20 ⁰ C was added Me ₃ SiOTf (62 μL, 0.34 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 177 as a foamy solid (2.68 g, 85%). MALDITOF-MS: Calcd for C ₁₂₈ H _12B O ₃₂ : 2176.84 [M] ⁺ ; Found 2199.90 [M + Na] ⁺ .

Preparation of (178) The mixture of compound 177 (185 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO.), and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 178 as a white solid (124 mg, 67%). MALDITOF-MS: Calcd for C ₁₂₈ Hi ₃₀ O ₃₂ : 2178.84 [M] ⁺ ; Found 2201.90 [M + Na] ⁺ . Preparation or (179) Compound 178 (120 mg, 0.055 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :1) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ¹ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 179 as an amorphous solid (55 mg, 97%): Selected ¹ H NMR (400 MHz ₁ C ₆ D ₅ N): 55.53 (d, 1 H, 72.5 Hz, H-I), 5.50 (d, 1 H, 72.6 Hz, H-I), 5.47 (d, 1 H, J2.5 Hz ₁ H-I), 5.09 (d, 1 H, J 7.2 Hz ₁ H-I). ¹³ C NMR (100 MHz, CD ₃ N): δ 105.5, 105.2, 104.1, 102.5. MALDITOF-MS: Calcd for C ₅₁ H ₈₆ O ₂ ,: 1034.57 [M] ¹ ; Found 1057.70 [M + Na] ⁺ .

Example 46

The preparation of

(25S)-26-0-α-L-fucopyranosyl-22-hydroxy-5β-fiιrostane- 3β,26-diol-3-0-P-D-glucopyran osyl-( 1 →4)-β-D-glucopyranosyl-(l -»4)-β-D-galactopyranoside (182) The overall reaction scheme is as follows:

Patent-scheme 46

Preparation of (180)

To a mixture of 73 (2.0 g, 1.7 mmol) and 168 (1.38 g, 1.55 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -20 ⁰ C was added NIS (562 mg, 2.5 mmol) and Me ₃ SiOTf (31 μL, 0.17 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 180 as a foamy solid (2.55 g, 83%). MALDTTOF-MS: Calcd for C ₁₀₇ H ₁₂₂ O ₃₆ : 1982.77 [M] ⁺ ; Found 2005.90 [M + Na] ⁺ . Preparation of (181)

The mixture of compound 180 (168 mg, 0.085 mrαol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic

layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 181 as a white solid (113 mg, 67%). MALDITOF-MS: Calcd for C ₁₀₇ H ₁₂₄ O ₃₆ : 1984.77 [M] ⁺ ; Found 2007.90 [M + Na] ⁺ . Preparation of (182)

Compound 181 (110 mg, 0.055 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1:0.5) indicated that the reaction was complete, The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 182 as an amorphous solid (56 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.53 (d, 1 H, / 2.5 Hz ₁ H-I) ₁ 5.28 (d, 1 H, J 6.9 Hz, H-I), 5.25 (d, 1 H, / 7.5 Hz, H-I) ₁ 5.09 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.2, 103.0, 102.5. MALDITOF-MS: Calcd for C _5I H ₈₆ O ₂₃ : 1066.56 [M] ⁺ ; Found 1089.70 [M + Na] ⁺ .

Example 47

The preparation of

(25S)-26-0-α-L-arabinopyranosyl-22-hydroxy-5β-furostane -3β,26-diol-3-0-β-D- galactopyranoside (188)

The overall reaction scheme is as follows:

Patent-scheme 47

Preparation of (185) To a mixture of compounds 4 (2.25 g, 4.1 mmol) and 183 (2,91 g, 4.8 mmol, commercially available) in anhyd CH ₂ Cl ₂ (36 mL) was added Me ₃ SiOTf (86 μL, 0.47 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 4:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with triethylaraine (TEA), then concentrated. Column chromatography (petroleum ether-EtOAc, 6:1) of the residue gave 184 as a foamy solid (3.45 g, 85%). To a solution of compound 184 (3.2 g, 3.2 mmol) in dry CH ₂ CIi (40 mL) was added BFj ¹ Et ₂ O (1.0 mL, 7.3 mmol), and the mixture was stirred at room temperature for 4 h, and TLC (petroleum ether-EtOAc, 1 :1) indicated that the reaction was complete. The mixture was diluted with CH ₂ Cl ₂ , washed with satd aq NaHCO ₃ and then satd aq NaCl. The organic layer was combined, dried, and concentrated. Purification by column chromatography (petroleum ether-EtOAc, 3:1) gave 185 as a white foamy solid (2.67 g, 95%): MALDITOF-MS: Calcd for C ₅₃ H ₆₄ O ₁₁ : 876.44 [M] ⁺ ; Found 899.50 [M + Na] ⁺ Preparation of (186) To a mixture of compound 87 (2.30 g, 3.10 mmol) and 186 (2.28 g, 2.6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was adde Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at

0 ⁰ C. The mixture was stirred under r.t. for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 2:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 186 as a foamy solid (3.41 g, 90%): MALDITOF-MS: Calcd for Cg ₇ H ₉ I)O ₂₀ : 1454.60 [M] ⁺ ; Found 1477.75 [M + Na] ⁺ . Preparation of (187)

The mixture of compound 186 (553 mg, 0.38 mmol) and NaBH ₄ (357 mg, 9.4 tnmol) in 2-propanol (16 mL) and CHiCh (2 mL) was stirred at room temperature for about 7.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1: 1) to give compound 187 as a white solid (360 mg, 65%): MALDITOF-MS: Calcd for C ₈₇ H ₉₂ O ₂₀ : 1456.60 [M] ⁺ ; Found 1479.75 [M + Na] ⁺ . Preparation of (188)

Compound 187 (189 mg, 0.13 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 24 mL), and then 1.0 M NaOMe in MeOH (0.25 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:0.5:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 188 as an amorphous solid (91 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): 55.25 (d,

1 H, J 7.5 Hz, H-I), 5.11 (d, 1 H, J 7.2 Hz ₁ H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.4, 102.5. MALDITOF-MS: Calcd for C ₃₈ H ₆₄ Oi ₃ : 728.43 [M] ⁺ ; Found 751.50 [M + Na] ⁺ .

Example 48

The preparation of

(25S)-26-0-α-L-arabinopyranosyI-22-hydroxy-5β-rurostane -3β,26-diol-3-0-β-D-glucopy ranosyl-(l -→2)-β-D-galactopyranoside (192) The overall reaction scheme is as follows

Patent-scheme 48

Preparation of (190)

To a mixture of compound 8 (1.38 g, 3.08 mraol) and 185 (2.28 g, 2.6 mmol) in anhyd CH ₂ Cl ₁ (50 mL) was added NIS (692 mg, 3.08 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 189 as a foamy solid (2.68 g, 82%): MALDITOF-MS: Calcd for C ₇₃ H ₈₂ O ₁₈ : 1246.55 [M] ⁺ ; Found 1269.70 [M + Na] ⁺ . Preparation of (190)

To a mixture of compound 10 (685 mg, 1.39 mmol) and 189 (1.43 g, 1.15 mmol) in anhyd CH ₂ CU (15 mL) was added Me ₁ SiOTf (26 μL, 0.14 mmol) under N ₂ atmosphere at - 42 ⁰ C. The mixture was stirred under these conditions for 30 min, at which time TLC

(petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, Then he mixture was concentrated with toluene and purified by column chromatography (petroleum ether-EtOAc, 3:1) to give 190 as a white foamy solid (1.35 g, 75%): MALDITOF-MS: Calcd for C ₈₇ H ₁₀₀ O ₂₇ : 1576.65 [M] ⁺ ; Found 1599.80 [M + Na] ⁴ . Preparation of (191)

The mixture of compound 190 (134 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 rnLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 191 as a white solid (85 mg, 65%): MALDITOF-MS: Calcd for C ₈₇ H ₁₀₂ O ₂₇ : 1578.65 [M] ⁺ ; Found 1601.80 [M + Na] ⁺ . Preparation of (192)

Compound 191 (79 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 192 as an amorphous solid (41 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ DjN): «55.40 (d, 1 H, J 6.7 Hz, H-I), 5.22 (d, 1 H, J l.2 Hz ₁ M-I), 5.10 (d, 1 H, J 7.5 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): £ 105.5, 103.8, 103.0. MALDITOF-MS: Calcd for C ₄₄ H ₇₄ O ₁₈ : 890.49 [M] ⁺ ; Found 913.55 [M + Na] ⁺ .

Example 49 The preparation of

(25S)-26-O-α-L-arabiπopyranosyl-22-hydroxy-5β-rurostan e-3β,26-diol-3-O-[α-L- rhamnopyranosyl-(l→4)]-[α-L-rhamnopyranosyl-(l->2)]-β -D-glucopyranoside (196)

The overall reacticm scheme is as follows:

Patent-scheme 49

Preparation of (193) To a mixture of 55 (996 rag, 2.30 mmol) and 185 (1.68 g, 1.92 mmol) in anhyd

CH ₂ Cl ₂ (20 mL) at -40 ⁰ C was added NIS (517 mg, 2.30 mmol) and Me ₃ SiOTf (42 μL, 0.23 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 193 as a foamy solid (1.91 g, 80%). MALDITOF-MS: Calcd for C ₇₃ H ₈₂ O ₁₈ : 1246.55 [M] ⁺ ; Found 1269.70 [M + Na] ⁺ . Preparation of (194)

To a mixture of 193 (1.80 g, 1.45 mmol) and 42 (2.16 g, 3.48 mraol) in anhyd CH ₂ Cl ₂ (30 mL) at -20 ⁰ C was added Me ₃ SiOTf (62 μL, 0.34 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 3:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 194 as a foamy solid (2.65 g, 85%). MALD1TOF-MS: Calcd for C ₁₂₇ H ₁₂₆ O ₃₂ : 2162.82 [M] ⁺ ; Found 2185.90 [M + Na] ⁺ .

Preparation of (195) The mixture of compound 194 (182 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO.), and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 195 as a white solid (121 mg, 67%). MALDITOF-MS: Calcd for C ₁₂₇ H ₁₂₈ O ₃₂ : 2164.82 [M] ⁺ ; Found 2187.90 [M + Na] ⁺ .. Preparation of (196) Compound 195(118 mg, 0.055 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :1) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 196 as an amorphous solid (52 mg, 97%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): <55.53 (d, 1 H, J 2.5 Hz, H-I), 5.49 (d, 1 H, J 2.6 Hz, H-I), 5.40 (d, 1 H, / 6.5 Hz, H-I), 5.09 (d, 1 H ₁ J 1,1 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 105.3, 104.4, 102.2. MALDITOF-MS: Calcd for C ₅₀ H ₈₄ O ₂₁ : 1020.55 [M] ⁺ ; Found 1043.70 [M + Na]'.

Example 50

The preparation of

(25S)-26-0-α-L-arabinopyranosyl-22-hydroxy-5β-furostane -3p,26-dioI-3-0-p-D-glucopy ranosyl-(l -»4)-β-D-glucopyranosyl-(l ->4)-β-D-galactopyranoside (199) The overall reaction scheme is as follows:

Patent-scheme 50

Preparation of (197)

To a mixture of 73 (2.0 g, 1.7 mmoi) and 185 (1.35 g, 1.55 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -20 ⁰ C was added NlS (562 mg, 2.5 mmol) and Me ₃ SiOTf (31 μL, 0.17 mmol) under N ₂ atmosphere at - 20 ⁰ C, The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 197 as a foamy solid (2.52 g, 83%). MALDITOF-MS: Calcd for C _I06 H _I2O O ₃₆ : 1968.76 [M] ⁺ ; Found 1991.85 [M + Na] ⁺ . Preparation of (198)

The mixture of compound 197 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ Cl ₂ (100 mLX 2), the combined organic

layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SCXi, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 :1) to give compound 198 as a white solid (111 mg, 67%). MALDITOF-MS: Calcd for Ci ₀₆ H ₁₂₃ O ₃₆ : 1970.76 [M] ⁺ ; Found 1993.85 [M + Na] ⁺ . Preparation of (199)

Compound 198 (110 mg, 0.055 mmol) was dissolved in anliyd CH ₂ Cl ₃ - MeOII (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 199 as an amorphous solid (54 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): (55.30 (d, 1 H, 77.5 Hz ₁ H-I) ₁ 5.28 (d, 1 H, J 6.1 Hz ₁ H-I), 5.25 (d, 1 H, J 7.2 Hz ₁ H-I) ₁ 5.09 (d, 1 H, J 7.7 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 104.8, 103.4, 102.7. MALDITOF-MS: Calcd for C ₅₀ H ₈₄ O ₂₃ : 1052.54 [M] ⁺ ; Found 1075.70 [M + Na] ⁺ .

Example 51

The preparation of

(25S)-26-O-β-D-xylopyranosyl-22-hyαjoxy-5β-rurostane-3 β,26-diol-3-O-β-D- galactopyranoside (205)

The overall reaction scheme is as follows:

Patent-schemeSl

Preparation of (202)

To a mixture of compounds 4 (2.25 g, 4.1 mmol) and 200 (2.91 g, 4.8 nunol, commercially available) in anhyd CH ₂ Cl ₂ (36 mL) was added Me ₃ SiOTf (86 μL, 0.47 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for

40 min, at the end of which time TLC (petroleum ether-EtOAc, 4:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with triethylamine (TEA), then concentrated. Column chromatography (petroleum ether-EtOAc, 6:1) of the residue gave 201 as a foamy solid (3.45 g, 85%).

To a solution of compound 201 (3.2 g, 3.2 mmol) in dry CH ₂ Cl ₂ (40 mL) was added BFs ¹ Et ₂ O (1.0 mL, 7.3 mmol), and the mixture was stirred at room temperature for 4 h, and TLC (petroleum ether-EtOAc, 1:1) indicated that the reaction was complete. The mixture was diluted with CH ₂ Cl ₂ , washed with satd aq NaHCOs and then satd aq NaCl. The organic layer was combined, dried, and concentrated. Purification by column chromatography (petroleum ether-EtOAc, 3:1) gave 202 as a white foamy solid (2.67 g, 95%): MALDITOF-MS: Calcd for C ₅₃ H ₆₄ O ₁₁ : 876.44 [M] ⁺ ; Found 899.50 [M + Na] ⁺ Preparation of (203)

To a mixture of compound 87 (2.30 g, 3.10 mmol) and 202 (2.28 g, 2,6 mmol) in anhyd CH ₂ Cl ₂ (50 mL) was adde Me ₃ SiOTf (56 μL, 0.31 mmol) under N ₂ atmosphere at

0 ⁰ C. The mixture was stirred under r.t. for 30 min, at the end of which time TLC

(petroleum ether-EtOAc, 2:1) indicated that all starting materials were consumed. The

reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 203 as a foamy solid (3.41 g, 90%): MALDITOF-MS: Calcd for C ₈₇ H ₉₀ O ₂₀ : 1454.60 [M] ⁺ ; Found 1477.75 [M + Na] ⁺ .

Preparation of (204) The mixture of compound 203 (553 mg, 0.38 mmol) and NaBH ₄ (357 mg, 9.4 mmol) in 2-propanol (16 mL) and CH ₂ Cl ₂ (2 mL) was stirred at room temperature for about 7.5 h. The reaction mixture was then extracted with CH ₁ CIa (100 mL X 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 204 as a white solid (360 mg, 65%): MALDITOF-MS: Calcd for C ₈₇ H ₉₂ O ₂₀ : 1456.60 [M] ⁺ ; Found 1479.75 [M + Na] ⁺ . Preparation of (205)

Compound 204 (189 mg, 0.13 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 24 mL), and then 1.0 M NaOMe in MeOH (0.25 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (H-BuOH-EtOH-H ₂ O ₁ 2:0.5:0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 205 as an amorphous solid (91 mg, 95%): Selected ¹ H NMR (400 MHz ₁ C ₆ D ₅ N): 65.25 (d, 1 H, J 6.9 Hz, H-I), 5.10 (d, 1 H, J 7.5 Hz, H-I). ¹³ C NMR (100 MHz, CD _S N): δ 105.5, 103.4. MALDITOF-MS: Calcd for C ₃₈ H ₆₄ Oi ₃ : 728.43 [M] ⁺ ; Found 751.50 [M + Na] ⁺ .

Example 52

The preparation of (25S)-26-O-β-D-xylopyranosyl-22-hydroxy-5β-fwostaπe-3β,2 6-diol-3-O-β-D-glucopyra nosyl-(l -→2)-β-D-galactopyranoside (209) The overall reaction scheme is as follows

Patent-scheme 52

Preparation of (206)

To a mixture of compound 8 (1.38 g, 3.08 mmol) and 202 (2.28 g, 2.6 mmol) in αnhyd CH ₂ Cl ₂ (50 mL) was added NIS (692 rag, 3.08 mmol) and Me ₃ SiOTf (55 μL, 0.30 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 206 as a foamy solid (2.68 g, 82%): MALDITOF-MS: Calcd for C ₇₃ Hg ₂ O ₁₈ : 1246.55 [M] ⁺ ; Found 1269.70 [M + Na] ⁺ . Preparation of (207)

To a mixture of compound 10 (685 mg, 1.39 mmol) and 206 (1.43 g, 1.15 mmol) in anhyd CH ₂ Cl ₂ (15 mL) was added Me ₃ SiOTf (26 μL, 0.14 mmol) under N ₂ atmosphere at - 42 ⁰ C. The mixture was stirred under these conditions for 30 min, at which time TLC

(petroleum ether-EtOAc, 1:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, Then he mixture was concentrated with toluene and purified by column chromatography (petroleum ether-EtOAc, 3:1) to give 207 as a white foamy solid (1.35 g, 75%): MALDITOF-MS: Calcd for C ₈₇ H ₁ QoO ₂₇ : 1576.65 [M] ⁺ ; Found 1599.80 [M + Na] ⁺ . Preparation of (208)

The mixture of compound 207 (134 rag, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-proρanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₃ Cl ₂ (100 tnLX2), die combined organic layer was washed with water (100 mLX3) and dried over anhydrous Na ₂ SO,), and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 208 as a while solid (85 mg, 65%): MALDITOF-MS: Calcd for C ₈₇ H ₁ O ₂ O ₂₇ : 1578.65 [M] ⁺ ; Found 1601.80 [M + Na] ⁺ . Preparation of (209)

Compound 208 (79 mg, 0.050 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (π-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 209 as an amorphous solid (41 mg, 95%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): £5.28 (d, 1 H, J 7.5 Hz, H-I), 5.24 (d, 1 H, 76.9 Hz, H-I), 5.10 (d, 1 H, /7.5 Hz ₁ H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 103.8, 103.0. MALDITOF-MS: Calcd for C ₄₄ H ₇₄ O ₁₈ : 890.49 [M] ⁺ ; Found 913.55 [M + Na] ⁺ .

Example S3 The preparation of

(25S)-26-O-β-D-xylopyranosy]-22-hydroxy-5β-furostane-3� �,26-diol-3-O-[α-L- rhamnopyranosyl-(l— )-4)]-[α-L-rhamnopyranosyl-(l->2)]-β-D-glucopyranoside (213)

The overall reaction scheme is as follows:

R R

Patent-schetne53

Preparation of (210)

To a mixture of 55 (996 mg, 2.30 mmol) and 202 (1.68 g, 1.92 mmol) in anhyd CH ₂ Cl ₂ (20 mL) at -40 ⁰ C was added NIS (517 mg, 2.30 mmol) and Me ₃ SiOTf (42 μL, 0.23 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 40 min, at the end of which time TLC (petroleum ether-EtOAc, 1 :1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 210 as a foamy solid (1.91 g, 80%). MALDITOF-MS: Calcd for C73H82O18: 1246.55 [M]+; Found 1269.70 [M + Na]+.

Preparation of (211)

To a mixture of 210 (1.80 g, 1.45 mmol) and 42 (2.16 g, 3.48 ramol) in anhyd CH ₂ Cl ₂ (30 mL) at -20 ⁰ C was added Me ₃ SiOTf (62 |LIL, 0.34 mmol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum etber-EtOAc, 3:1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2:1) of the residue gave 211 as a foamy solid (2.65 g, 85%). MALDITOF-MS: Calcd for C ₁₂₇ H ₁₂₆ O ₃₂ : 2162.82 [M] ⁺ ; Found 2185.90 [M + Na] ⁺ .

Preparation of (212) The mixture of compound 211 (182 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 ramol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ CIi (100 mLX 2), the combined organic layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO,!, and the solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1:1) to give compound 212 as a white solid (121 mg, 67%). MALDITOF-MS: Calcd for C ₁₂₇ H ₁₂₈ O ₃₂ : 2164.82 [M] ⁺ ; Found 2187.90 [M + Na] ⁺ .. Preparation of (213) Compound 212(118 rag, 0.055 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1:2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1: 1) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 213 as an amorphous solid (52 mg, 97%): Selected ¹ H NMR (400 MHz, C ₆ D ₅ N): δ 5.55 (d, 1 H, J 2.5 Hz, H-I), 5.50 (d, 1 H, J 2.9 Hz, H-I), 5.10 (d, 1 H, / 7.5 Hz, H-I), 5.05 (d, 1 H, J 7.2 Hz, H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 105.5, 104.8, 103.2, 103.1. MALDITOF-MS: Calcd for C _S0 H ₈₄ O _2I : 1020.55 [M] ⁺ ; Found 1043.70 [M + Na] ⁺ .

Example 54

The preparation of (25S)-26-

0-P-D-xylopyranosyl-22-hydroxy-5β-fυrostane-3β,26-diol -3-0-β-D-glucopyranosyl-(l →4)-β-D-gIucopyranosyl-( 1 →4)-β-D-galactopyranoside (216) The overall reaction scheme is as follows:

Patent-scheme 54

Preparation of (214)

To a mixture of 73 (2.0 g, 1.7 πunol) and 202 (1.35 g, 1 .55 mraol) in anliyd CH ₂ Cl ₂ (20 mL) at -20 ⁰ C was added NIS (562 mg, 2.5 mmol) and Me ₃ SiOTf(Sl ^LL ₁ 0.17 ππnol) under N ₂ atmosphere at - 20 ⁰ C. The mixture was stirred under these conditions for 30 min, at the end of which time TLC (petroleum ether-EtOAc, 1 : 1) indicated that all starting materials were consumed. The reaction mixture was neutralized with TEA, then concentrated. Column chromatography (petroleum ether-EtOAc, 2: 1) of the residue gave 214 as a foamy solid (2.52 g, 83%). MALDITOF-MS: Calcd for C ₁₀₆ Hu ₀ O ₃₆ : 1968.76 [M] ⁺ ; Found 1991.85 [M + Na]'. Preparation of (215)

The mixture of compound 214 (165 mg, 0.085 mmol) and NaBH ₄ (96 mg, 2.5 mmol) in 2-propanol (8 mL) and CH ₂ Cl ₂ (1 mL) was stirred at room temperature for about 8.5 h. The reaction mixture was then extracted with CH ₂ C] ₂ (100 mLX 2), the combined organic

layer was washed with water (100 mLX 3) and dried over anhydrous Na ₂ SO ₄ , and lhe solvent was removed under vacuum to give an colorless oil, which was purified by column chromatography (petroleum ether/ethyl acetate, 1 : 1} to give compound 215 as a white solid (111 mg, 67%). MALDITOF-MS: Calcd for C ₁₀₆ Hi ₂₂ O ₃₆ : 1970.76 [M] ⁺ ; Found 1993.85 [M + Na] ⁺ . Preparation of (216)

Compound 215 (110 mg, 0.055 mmol) was dissolved in anhyd CH ₂ Cl ₂ - MeOH (1 :2, 18 mL), and then 1.0 M NaOMe in MeOH (0.2 mL) was added at 0 ⁰ C. After stirring at room temperature for 5 h, TLC (n-BuOH-EtOH-H ₂ O, 2:1 :0.5) indicated that the reaction was complete. The solution was neutralized with ion-exchange resin (H ⁺ ), and then filtered and concentrated. The residue was purified by Bio-gel P ₂ column to afford 216 as an amorphous solid (54 mg, 96%): Selected ¹ H NMR (400 MHz, C ₆ D ₃ N): <55.27 (d, 1 H, 77.5 Hz, H-I), 5.24 (d, 1 H ₁ / 6.9 Hz, H-I), 5.14 (d, 1 H ₁ J 7.5 Hz, H-I) ₁ 5.06 (d, 1 H ₁ J 12 Hz ₁ H-I). ¹³ C NMR (100 MHz, CD ₅ N): δ 103.6, 103.3, 103.0, 102.4. MALDITOF-MS: Calcd for Cs ₀ H ₈₄ O ₂₃ : 1052,54 [M] ⁺ ; Found 1075.70 [M + Na] ⁺ .

The foregoing broadly defines the present invention without limitation. Variations and modifications as will be readily apparent to those skilled in this art are intended to be included within the present invention as defined in the appended claims.