The present invention relates to a method for preparing polyfluorinated compounds .

Aromatic ring systems comprising functional groups with polyfluorinated heteroatoms have very promising applications in contemporary medicinal chemistry, agrochemistry, as chemical building blocks, as reagents and for advanced materials, such as liquid crystals.

Historically, synthetic fluorine chemistry has often relied on hazardous reagents and specialized apparatuses. For example, in the case of aryl pentafluorosulfanyl-containing (SF5) compounds, early reports involved using high-energy reagents such as F2 or XeF2. Said reagents are toxic, explosive and corrosive, and the yield of the products obtained when using such high-energy reagents is relatively low. In addition, handling of gas reagents, such as F2, is expensive when considering their production, storage and use. Alternatively, aryl pentafluorosulfanyl-containing (SF5) compounds or precursors thereof can be obtained involving SF5CI. Up to now, SF5CI is extremely expensive and difficult to obtain.

EP 2 468 720 discloses the synthesis of aryl-SFs compounds in a two-step protocol from diaryl disulfides:

There are several established methods for the second step, i.e. the Cl-F exchange. However, the first step of this procedure, i.e. to access aryl tetrafluoro-X ⁶ -sulfanyl chloride compounds (aryl-SF4Cl) , requires handling of chlorine gas in combination with a metal fluoride. Chlorine gas is a very reactive, corrosive reagent and difficult to handle.

US 2005/012072 discloses aryl trifluoromethoxytetrafluoro- sulfuranes, which may be derivatized to yield highly electrically polar molecules. US 2012/083627 discloses a method of preparing 2 , 6~dimethyl-4-t- butylphenylsulfur trifluoride by reacting an alkali metal fluoride, bis (2 , 6-dimethyl-4-t-butylphenyl ) disulfide and bromine .

WO 2009/152385 discloses methods for the synthesis of fluoro- sulfur compounds, more specifically of SF4, SF5CI, SFsBr and SF ₆ . The method involves admixing Br2, a metal fluoride reactant, and a sulfur reactant thereby initiating a reaction that produces a yield of the fluoro-sulfur compound of greater than about 10%.

US 3,035,890 discloses a method for preparing SF5CI by reacting CIF3 with elementary sulfur under anhydrous conditions while maintaining the temperature between 15°C and 105°C. Chlorine trifluoride is a poisonous, corrosive, and extremely reactive gas . The problem of the present invention is to provide a method for preparing polyfluorinated compounds without using corrosive and toxic gaseous reagents.

The problem is solved by the method according to the present invention. Further preferred embodiments are subject of the dependent claims .

The process according to the present invention provides a safe method for preparing a polyfluorinated compound of formula

Ar-Ri (I), wherein Ar-Ri (I) is an aromatic ring system wherein

Ri is selected from the group consisting of SF ₄ CI, SF ₃ , SF ₂ CF ₃ , TeFs, TeF ₄ CF ₃ , SeF ₃ , SeF ₂ CF ₃ , IF ₄ , and IF ₂ ,

X ₂ is N or CR ₂ ,

X ₃ is N or CR ₃ ,

X ₄ is N or CR ₄ ,

X ₅ is N or CR ₅ ,

X ₆ is N or CR ₆ , and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3, wherein R ₂ , R ₃ , R ₄ , R5 and R ₆ are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl , 2 , 2 , 2-trifluoroethyl , pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl , methylcarbonyl, ethylcarbonyl , acetoxy, t-butyl, phenylcarbonyl , benzylcarbonyl, 3-trifluoromethylphenyl , phenylsulfonyl , methylsulfonyl , chlorophenyl , methyldoxolonyl , methyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoromethyl, fluoroethyl and phenyl, or if X ₅ is CR ₅ and Ce is CR ₆ R ₅ and R ₆ may form together a saturated or unsaturated five or six membered ring system comprising one or more nitrogen, wherein said five or six membered ring system may be substituted with one or more residues R ₇ having the same definition as R ₂ to R ₆ , and with the proviso that if Ri is SF ₃ , at least one of R ₂ and Re is neither hydrogen nor fluoro and if Ri is not SF3, R2 and R ₆ are independently from each other either hydrogen or fluoro and if at least one of X ₂ , X ₃ , X ₄ , X ₅ and Xe is nitrogen, at least one of R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is not hydrogen.

Said process involves the following reaction step: Reacting a starting material selected from the group consisting of Ar ₂ S ₂ , Ar ₂ Te ₂ , Ar ₂ Se ₂ , ArSCF ₃ , ArTeCFs, Arl, ArSeCF ₃ , ArSCH ₃ , and Ar-SCl, wherein Ar has the same definition as above, and with trichloroisocyanuric acid (TCICA) of the formula (III)

in the presence of an alkali metal fluoride (MF) , preferably potassium fluoride (KF) .

The method according to the present invention allows a gas reagent-free synthesis of polyfluorinated compounds and in particular of Ar-SF ₄ C1 compounds in competitive yields using easy-to-handle trichloroisocyanuric acid as an inexpensive oxidant/chlorine source and an alkali metal fluoride. Trichloroisocyanuric acid is a bench-stable, commercially available and cheap solid compound. The method according to the present invention allows the access to a variety of aromatic and heteroaromatic aryl-SF _i Cl compounds in high yields. Said aryl- SF ₄ CI compounds can then subsequently be converted to aryl-SFs compounds or aryl-SFiRio compounds via established synthetic routes. Preferably, the alkali metal fluoride is potassium fluoride due to its lower cost and commercial availability.

In the context of the present invention, the term "aryl" is intended to mean an aromatic ring having six carbon atoms.

In the context of the present invention, the term "heteroaryl" is intended to mean an aryl group where one or more carbon atoms in the aromatic ring have been replaced with one or more nitrogen atoms .

In the context of the present invention, the term "aromatic ring system "Ar"" herein means both, "aryl" and "heteroaryl".

The method according to the present invention is preferably carried out in presence of a catalytic amount of a Bronsted or Lewis acid. Such a Bronsted or Lewis acid is preferably selected from the group consisting of trifluoroacetic acid (TFA) , aluminum chloride (AICI ₃ ) , aluminum bromide (AlBr ₃ ) , boron trifluoride (BF ₃ ) , tin dichloride (SnCl ₂ ) , zinc chloride (ZnCl ₂ ) and titanium tetrachloride (TiCli) or a mixture thereof, preferably ZnCl ₂ and TFA, most preferably TFA.

Preferably, the Bronsted or Lewis acid, and in particular TFA, is present in the process according to the present invention between 5 mol% and 15 mol%, preferably 10 mol%. Larger quantities of the Br0nsted or Lewis acid result in substantial yield loss or complete inhibition of product formation.

Preferably, the molar ratio of TCICA:MF present in the process according to the present invention, is between 1:1 and 1:10, most preferably 1:1 and 1:5, and ideally 1:2 since excessive TCICA can result in additional putative ring chlorination. Very good results can be obtained for example in reaction conditions comprising 18 equivalents of TCICA, 32 equivalents of the alkali metal fluoride (MF) , and 10 mol% of TFA in acetonitrile (MeCN) . Preferably, the method according to the present invention is carried out at room temperature in order to avoid additional ring chlorination which may be observed when heating the reaction mixture to about 45 °C. The solvent is preferably a polar aprotic solvent, most preferably selected from the group consisting of ethyl acetate, pivalonitrile and acetonitrile, ideally acetonitrile (MeCN) .

Preferably, the metal fluorides, and in particular KF, are dried in advance under inert atmosphere resulting in higher yields than standard MF which have not been dried before using. Most preferably, MF and in particular KF is spray-dried since the consistent particle size distribution positively influences the reaction .

In one embodiment of the present invention, the method relates to the preparation of Ar-Ri (I), wherein Ar and Ri have the same definition as above.

Preferably, the process according to the present invention is used to prepare a compound of formula (I) , wherein Ri is SF ₄ CI or SF ₃ , preferably SF ₄ CI due to its synthetic importance as chemical building block. In one embodiment of the present invention, Ri is SF ₄ CI. Aryl- or heteroaryl tetrafluorohalosulfanyl-containing compounds of formula Ar-SF ₄ C1 (IV) include isomers such as cis-isomers (IVa) and trans-isomers (IVb) as shown below:

Ar-SF ₄ C1 is obtained by the method according to the present invention by reacting the corresponding diaryl or heteroaryl disulfide with TCICA and the alkali metal fluoride (MF) (scheme 1) . Optionally, a Bronsted or Lewis acid is present as well. (scheme 1)

Preferably the alkali metal fluoride is KF. In the aromatic ring system, R ₃ , R ₄ , and R ₅ are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2 , 2 , 2-trifluoroethyl , pentafluorosulfanyl , phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, methoxycarbonyl , ethoxycarbonyl, methylcarbonyl, ethylcarbonyl , acetoxy, t-butyl, phenylcarbonyl, benzylcarbonyl, 3-trifluoromethylphenyl , phenylsulfonyl , methylsulfonyl, chlorophenyl , methyldoxolonyl, methyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoromethyl, fluoroethyl and phenyl, or if X ₅ is CR ₅ and Xe is CR ₆ R ₅ and Re may form together a saturated or unsaturated five or six membered ring system comprising one or more nitrogen, wherein said five or six membered ring system may be substituted with one or more residues R ₇ having the same definition as R ₂ to R ₆ , and

R ₂ and R ₆ are independently from each other either hydrogen or fluoro. Most preferably, R2 is hydrogen or fluoro and R ₆ is hydrogen. Surprisingly, it is also possible to carry out the method according to the present invention if a mild donating group such as a t-butyl group was present in the aromatic ring system. This residue precludes benzylic chlorination and undergoes only minor ring chlorination. Preferably, the aromatic ring system is selected from the group consisting of phenyl, pyridinyl, pyrimidinyl and 2,3,5- triazine, most preferably phenyl . Ar-SF4C1 is a very important intermediate product and can be converted into other important synthetic building blocks by a subsequent reaction step, so that the overall reaction is as follows (scheme 2) :

one step (scheme 2)

Thus, another embodiment of the present invention relates to the use of Ar-SF4 as starting material to obtain a compound of formula (V) or (VI)

wherein

X2 is N or CR2,

X ₃ is N or CR ₃ ,

X4 is N or CR ₄ ,

X ₅ is N or CR ₅ , C _d is N or CR ₆ , and the total number of nitrogen atoms in the aromatic ring system is between 0 and 3,

R2 and R ₆ are independently from each other either hydrogen or fluoro and R ₃ , R ₄ , and R ₅ are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2 , 2 , 2-trifluoroethyl , pentafluorosulfanyl , phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, methoxycarbonyl , ethoxycarbonyl , methylcarbonyl, ethylcarbonyl, acetoxy, t-butyl, phenylcarbonyl , benzylcarbonyl, 3-trifluoromethylphenyl , phenylsulfonyl , methylsulfonyl, chlorophenyl , methyldoxolonyl , methyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoromethyl , fluoroethyl and phenyl, or if X ₅ is CR ₅ and Ce is CR ₆ R ₅ and R ₆ may form together a saturated or unsaturated five or six membered ring system comprising one or more nitrogen, wherein said five or six membered ring system may be substituted with one or more residues R _? having the same definition as R ₂ to R ₆ , and

Rio is linear or branched, substituted or unsubstituted alkyl, cx- alkenyl or a-alkynyl having 2 to 10 carbon atoms.

Thus, one embodiment of the present invention relates to the preparation of the compound of formula (VI) (Ar-SF ₄ Rio) . Ar-SF ₄ C1 obtained by the method according to the present invention can subsequently be converted in a second step to Ar-SF ₄ Rio by using the well-known BEt ₃ chemistry (Das et al, Org. Chem. Front.,

2018, 5, 719-724 and Zhong et al, Angew. Chem. Int. Ed., 2014, 53, 526-529) . Rio is a linear or branched, substituted or unsubstituted alkyl, cx-alkenyl or cx-alkynyl group having 2 to 20 carbon atoms. For synthetic reasons, the alkyl or a-alkenyl comprise preferably a chlorine residue in b-position. The term "a-alkenyl" group stands for an alkenyl group the double bond of which is directly linked to the sulfur atom and the term "cx- alkynyl" group stands for an alkynyl group the triple bond of which is directly linked to the sulfur atom. In case of an alkyl group, Rio is preferably selected from the group consisting of 2-chloro-ethyl, 2-chloro-propyl, 2-chloro-2~ phenyl-ethyl, 2-chloro-butyl , 2-chloro-4-phenyl-butyl , 2-chloro- pentyl, 2-chloro-2-cyclohexyl-ethyl , 2-chloro-2- ( 4- cyclohexylphenyl) -ethyl and 2-chlorohexyl .

In case of an a-alkenyl group, Rio is preferably selected from the group consisting of 2-chloro-ethenyl , 2-chloro-propenyl , 2- chloro-2-phenyl-ethenyl, 2-chloro-butenyl , 2-chloro-4-phenyl- butenyl, 2-chloro-pentenyl , 2-chloro-2-cyclohexyl-ethenyl , 2- chloro-2- (4-cyclohexylphenyl) -ethenyl and 2-chlorohexenyl .

In case of an a-alkynyl group, Rio is preferably selected from the group consisting of ethynyl, propynyl, 3-phenyl-propynyl , 3- cyclohexyl-propynyl, 3- ( 4-cyclohexylphenyl ) -propynyl , butynyl, pentynyl, hexynyl, heptynyl and octynyl . An a-alkynyl group can be obtained by reacting the corresponding alkyne in the presence of catalytic amounts of BEt3 and subsequent chloride elimination (scheme 3) :

(scheme 3) The reaction conditions are known from literature such as in Zhong, L. et al, Angew. Chem. Int . Ed. 2014, 53, 526-529 and Das, P. et al, Org. Chem. Front., 2018, 5, 719-724.

An a-alkenyl group can be obtained by reacting the corresponding alkyne in the presence of catalytic amounts of BEt3 (scheme 4) :

H - = - R10' (scheme 4) An alkyl group can be obtained by reacting the corresponding alkene in the presence of catalytic amounts of BEt3 (scheme 5) :

(scheme 5)

Further, as shown in scheme 6, another embodiment of the present invention relates to the preparation of compounds Ar-Ri, wherein Ri is SF5 (formula (IV) . Ar-SF ₄ C1 obtained by the method according to the present invention can be converted to Ar-SFs by reacting said compound with silver (I) fluoride at elevated temperature, for example at 120°C (Kanishchev et al, Angew. Chem. Int. Ed., 2015, 54, 280-284) .

AgF

heat (scheme 6)

This two-step method for preparing the Ar-SFs derivatives significantly reduces the number of synthetic and purification steps from previously reported syntheses. In particular, said reaction step is possible as well if a carbon atom of the ring system is substituted with an acetoxy group, as shown, for example, for the acetoxy group being located in para position of the tetrafluoro-A6-sulfanyl chloride group (scheme 7) .

wor up (scheme 7)

Preferably, a mild saponification procedure such as a LiOH workup of the crude reaction mixture can be carried out to provide direct access to the corresponding

(pentafluorosulfanyl) phenol . Thus, said procedure can be generalized to obtain polyfluorinated phenols, hydroxypyridines , hydroxypyrimidines and hydroxytriazines . Another embodiment of the present invention relates to the production of compounds Ar-Ri, wherein Ri is SF ₃ . As the method according to the present invention can also be used to access the S ⁺⁴ oxidation state on substrates that contain ortho residues selected from the groups consisting of chloro, bro b, nitro, trifluoromethyl, 2, 2, 2-trifluoroethyl, methoxycarbonyl, ethoxycarbonyl, acetoxy, pentafluorosulfanyl, t-butyl and phenyl (scheme 8) . In general, in order to obtain Ar-SF ₃ , at least one of R ₂ or R ₆ must not be hydrogen or fluorine. (scheme 8) Preferably, R ₂ and/or R ₆ are electron-withdrawing groups such as chloro, bromo, and nitro. Most preferably, R ₂ is chloro or nitro and R ₆ is hydrogen. In addition, in the aromatic ring system R ₃ , R ₄ , and R ₅ are independently selected from the group consisting of hydrogen, fluoro, chloro, bromo, nitro, trifluoromethyl, 2, 2, 2-trifluoroethyl, methoxycarbonyl, ethoxycarbonyl, acetoxy, pentafluorosulfanyl, t-butyl and phenyl.

Another embodiment of the present invention relates to the preparation of compounds Ar-Ri, wherein Ri is SF ₂ CF ₃ . Ar-SF ₂ CF ₃ is obtained by the method according to the present invention by reacting the corresponding aryl trifluoromethyl sulfide Ar-SCF ₃ with TCICA and the alkali metal fluoride (MF) (scheme 9) . Optionally, a Bronsted or Lewis acid is present as well. (scheme 9)

Preferably, the alkali metal fluoride is KF. Ar-SF ₂ CF3 may be used as fluorinating agent.

Another embodiment of the present invention relates to the production of compounds Ar-Ri, wherein Ri is IF ₂ . Ar-IF ₂ is obtained by the method according to the present invention by reacting the corresponding ortho-, meta- or para-substituted aryl iodide Ar-I with TCICA and the alkali metal fluoride (MF) (scheme 10a) . Especially good results could be obtained with ortho-substituted aryl iodines. Optionally, a Bronsted or Lewis acid is present as well.

(scheme 10a)

Preferably, the alkali metal fluoride is KF. Ar-IF ₂ is an interesting chemical building block and fluorinating reagent.

Alternatively, Ar-I may be used as starting material of the method according to the present invention to prepare Ar-IF ₄ . Ar- IF ₄ is obtained by the method according to the present invention by reacting the corresponding meta- or para-substituted aryl iodide Ar-I with TCICA and the alkali metal fluoride (MF) (scheme 10b) . In case of an ortho-substituted aryl iodide, the substitutent in ortho position should be hydrogen or fluoride. Optionally, a Bronsted or Lewis acid is present as well. cond.

In one embodiment of the present invention, the aromatic ring system of the compound of formula (I) is a substituted or unsubstituted phenyl ring and Ri to Re have the same definition as above (compound of formula (la)):

In another embodiment of the present invention, at least one of X ₂ , X ₃ , X ₄ , X ₅ and Ce in the compound of formula (I) is nitrogen, that is, the aromatic ring system is a heteroaromatic ring system. Preferably, exactly one of X ₂ , X ₃ , X ₄ , X ₅ and Xe is nitrogen, that is, the aromatic ring system of the compound of formula (I) is a pyridyl ring and R ₂ to R ₆ have the same definition as above. Preferably, the nitrogen atom of the pyridine ring system is in position 2 (X ₂ ) (compound of formula

(lb) . By substituting the pyridyl ring with an electron- withdrawing group, e.g. a bromine or nitro group, the corresponding heteroaryl-Ri compounds, in particular heteroaryl- SF ₄ CI compounds, are accessible in good yields.

In one embodiment of the present invention, exactly two of X ₂ , X ₃ , X ₄ , X ₅ and Ce in the compound of formula are nitrogen, preferably X ₂ and Cb (compound of formula (Ic) ) :

Pyrimidinyl rings substituted with electron-withdrawing groups, e.g. bromine or nitro groups, resulted in the corresponding heteroaryl-Ri compounds, in particular heteroaryl-SFiCl compounds, in good yields as well.

In one embodiment of the present invention, exactly three of X ₂ , X3, X4, X5 and Ce are nitrogen, preferably X ₂ , X3 and Cb (compound of formula (Id) ) :

For example, the disulfide derived from 5 , 6-diphenyl-l , 2 , 4- triazine-3-thiol, resulted in the corresponding 5, 6-diphenyl- 1 , 2 , 4-triazine-3-sulfur chlorotetrafluoride in 67% yield:

Preferably, in the compound of formula (I) at least one of R ₂ , R ₃ , R ₄ , Rs and R ₆ is fluoro, chloro, bromo, methoxycarbonyl , ethoxycarbonyl or acetoxy, preferably chloro or bromo since it has been shown that the method according to the present invention results in very good yields for aromatic ring systems with electron-withdrawing groups. However, the method according to the present invention does not work in case of free carboxy and free hydroxy groups. Though, this can be circumvented by converting the carboxy group, for instance, to the corresponding methyl ester and ethyl ester or to the corresponding acetal and by converting the hydroxy group, for instance, to the corresponding acetoxy group. Further suitable protecting groups are known to the skilled person. The compatibility of esters under these reaction conditions according to the present invention is a significant advantage over the CI2/KF protocol disclosed in EP 2 468 720, which cannot demonstrate the compatibility of esters.

In another embodiment of the present invention, the starting material is a diaryl dichalcogenide selected from the group consisting of Ar2S2, Ar2Te2 and Ar2Se2, preferably Ar2S2. Most of the diaryl dichalcogenides are commercially available starting materials which are easy to handle. In particular, diaryl disulfides are common sources of the aryl sulfide units in organic synthesis.

In another embodiment of the present invention, Ar-SFiCl can be prepared by using Ar-SCl or Ar~SCH3 as starting material. One advantage to using either of these starting materials in place of diaryl disulfides lies in synthetic accessibility, as diaryl disulfide substrates with higher molecular weights may be more difficult to synthesize and / or purify.

In another embodiment, the starting material of the method according to the present invention is the diaryl chalcogenide Ar2Te resulting in a diaryl tetrafluoro-A6-tellane-compound, which may be used as liquid crystals.

In another embodiment, the starting material of the method according to the present invention is ArSeCF3 resulting in a difluoro (aryl) (trifluoromethyl) -A4-selane compound, which may be used, for example, as synthetic building blocks for selenium containing pharmaceuticals. In another embodiment, the starting material of the method according to the present invention is Ar- SCF3 resulting in Ar-SF2CF3 which may be used, for example, as a fluorinating agent. In another embodiment of the present invention the starting material of the method according to the present invention is Arl since this allows a F2- and HF-free synthesis of Ar-IF2 compounds . Another embodiment of the present invention relates to a safe method for preparing the polyfluorinated compound SF5CI (II) . Said process involves the following reaction step:

Reacting the starting material Se with trichloroisocyanuric acid (TCICA) of the formula (III)

in the presence of an alkali metal fluoride (MF) , preferably potassium fluoride (KF) . In particular, said process for preparing SF5CI is carried out by reacting Ss and trichloroisocyanuric acid and the alkali metal fluoride (MF) . Optionally, a Bronsted or Lewis acid is present as well. Preferably, the alkali metal fluoride is KF. This synthesis allows the in situ preparation of SF ₅ CI which is under normal circumstances extremely difficult to obtain and to handle. The SF ₅ CI gas thus obtained can be used to carry out further chemical reaction. Preferably, the SF ₅ CI gas thus obtained is directly used for further reaction without purification.

Another embodiment of the present invention relates to a safe method for preparing the polyfluorinated compound CF ₃ SF ₄ CI. Said process involves the following reaction step: Reacting the starting material Ar-S-S-CF ₃ , wherein Ar has the same definition as above, with trichloroisocyanuric acid (TCICA) of the formula (III)

in the presence of an alkali metal fluoride (MF) , preferably potassium fluoride (KF) . Preferably, Ar is phenyl or a para- nitro-phenyl . In particular, said process for preparing CF ₃ SF ₄ CI is carried out by reacting Ar-S-S-CF ₃ and trichloroisocyanuric acid and the alkali metal fluoride (MF) . Optionally, a Br0nsted or Lewis acid is present as well. Preferably, the alkali metal fluoride is KF. This synthesis allows the in situ preparation of CF ₃ SF ₄ CI. The CF ₃ SF ₄ CI gas thus obtained can be used to carry out further chemical reaction, in particular for the preparation of novel materials or biologically active agents comprising this extraordinarily lipophilic and profoundly electron withdrawing group. Preferably, the CF ₃ SF ₄ CI gas thus obtained is directly used for further reaction without purification.

By the method of the present invention the following compounds of formula (I)

may preferably be obtained in a very easy way:

The compounds obtained by the method according to the present invention may be used as synthetic building blocks, pharmaceuticals, materials, reagents, and agrochemicals. Another aspect of the present invention relates to the following new compounds of formula (I)

said compounds being selected from the group consisting of

All compounds disclosed in the above list may be used for example as synthetic building blocks, pharmaceuticals, agrochemicals and advanced materials such as liquid crystals. Experiments

Example 1: General Procedure for Synthesis of Aryl Tetrafluoro- X ⁶ -sulfanyl Chloride Compounds cond

,S CI

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the disulfide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

In order to remove KF and TCICA (and its byproducts) outside of the glove box, the crude reaction mixture was first filtered into a polyethylene centrifuge tube and concentrated by blowing N ₂ over it. Then, it was diluted with dry pentane, filtered into a polyethylene centrifuge tube, and concentrated by blowing N ₂ over it. The crude material consisted of mostly the aryl- SF ₄ CI product (amount quantified by ¹⁹ F NMR) and was carried forward without further purification.

Alternatively, for more moisture sensitive products, the reaction vessel atmosphere was purged with Ar and transported into the glovebox. Subsequently, the crude reaction mixture was filtered into a PFA vessel via syringe filter and concentrated in vacuo. Then, it was diluted with dry hexanes, filtered into a PFA vessel, and concentrated in vacuo. The crude material consisted of mostly the aryl-SF ₄ Cl product (amount quantified by ¹⁹ F NMR) and was carried forward without further purification.

Representative Product

70% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ^1S F NMR (377 MHz, CD ₃ CN) : +136.61 (4F, s) .

Example 2: General Procedure for Synthesis of Aryl Sulfur Trifluoride Compounds cond

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv. ) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N ₂ atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the disulfide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Note that substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination .

Representative Product

92% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure. ¹⁹ F NMR (471 MHz, CD ₃ CN) : +63.46 (2F, d, J = 75.6 Hz), -56.31 (IF, t, J = 75.6 Hz).

Example 3 : General Procedure for Synthesis of Aryl Selenium Trifluoride Compounds cond

SeF ₃

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere . Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the diselenide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

Representative Product 95% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure. The product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : -25.51 (3F, br s) .

Example 4 : General Procedure for Synthesis of Aryl Pentafluorotelluryl Compounds co d

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the ditelluride substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

Representative Product

>90% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure. The product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -37.60 (IF, quint, J = 148.6 Hz), -54.50 (4F, quint, J = 148.6 Hz).

Example 5: General Procedure for Synthesis of

Difluoro (aryl) (trifluoromethyl) -A ⁴ -sulfane Compounds

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl (trifluoromethyl) sulfane substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

Representative Product 81% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -14.38 (2F, q, J =

18.0 Hz), -62.79 (3F, t, J = 18.0 Hz).

Example 6: General Procedure for Synthesis of

Tetrafluoro (aryl) (trifluoromethyl) -X ⁶ -tellane Compounds d

TeF ₄ CF ₃

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl (trifluoromethyl) tellane substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

Representative Product

>95% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -54.10 (3F, quint, J = 22.5 Hz), -68.73 (4F, q, J = 22.5 Hz).

Example 8 : General Procedure for Synthesis of Aryl

Difluoroiodane Compounds cond.

Trichloroisocyanuric acid (0.32 g, 1.4 mmol, 6.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.07 g, 1.2 mmol, 5.0 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl iodide substrate (0.23 mmol, 1.0 equiv.) in 2.0 mL MeCN was added to the vial, and the reaction mixture was stirred at 40 °C for ca. 24 h. Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 L internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

Representative Product

97% yield (by ¹⁹ F NMR) . The reaction was run according to the general procedure. The product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -97.44 (2F, t, J = 2.3 Hz), -165.67 (2F, t, J = 2.3 Hz).

Example 9: Procedure for Synthesis of SF ₅ Cl

cond.

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, followed by elemental sulfur (0.46 mmol, 1.0 equiv.). The reaction vessel was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Upon reaction completion, the head space of the vial was drawn up into a syringe for GC/MS analysis. Subsequently, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for ¹⁹ F NMR analysis.

The product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : 124.26 (4F, d,

_< 7= 151.2 Hz), 64.15 (IF, d, J = 151.2 Hz).

Example 10: General Procedure for Synthesis of

Pentafluorosulfanyl Compounds A solution of a known amount of aryl-SF4Cl compound (1.0 equiv.) in anhydrous CH2CI2 was transferred to a copper (or PFA) vessel and concentrated. Subsequently, AgF (2.0 equiv.) was added, and the reactor was sealed under Ar atmosphere. The sealed reactor was heated to 120 °C for ca . 2 days. Upon cooling, the reactor was rinsed with copious amounts of CH2CI2 and H2O into a separatory funnel. The reaction mixture was extracted with CH2CI2. The combined organic layers were dried with MgS0 ₄ , filtered through Celite, and concentrated. The crude reaction mixture was purified via gradient column chromatography on a Teledyne-Isco Combiflash instrument, eluting with hexanes : EtOAc .

Representative Product

77% yield (isolated) . The reaction was run according to the general procedure using AgF in a copper vessel; the product was isolated via gradient column chromatography on silica gel in as a white solid. ¹⁹ F NMR (377 MHz, CDC1 ₃ ) : 84.32 (IF, quint, J = 150.6 Hz), 63.62 (4F, d, J = 150.6 Hz); ¾ NMR (400 MHz, CDC1 ₃ ) : 7.78 (2H, dm, J = 9.1 Hz), 7.20 (2H, d, J = 9.1 Hz), 2.33 (3H, s); ¹³ C{ ^:l H} NMR (101 MHz, CDC1 ₃ ) : 168.7, 152.5, 150.9 (quint, J = 18.0 Hz), 127.5 (quint, J= 4.8 Hz), 121.8, 21.0. Example 11: General Procedure for Synthesis of Aryl Tetrafluoro- X ⁶ -sulfanyl Chloride Alkanes/Alkenes

R = alkyl, alkenyl, etc.

A solution of a known amount of aryl-SFiCl compound (1.0 equiv.) in anhydrous CH2CI2 (0.05-0.1 M) was transferred to a PFA vessel equipped with a stir bar under Ar atmosphere. The alkene or alkyne substrate (1.5 equiv.) was added, followed by 10 mol % BEt ₃ (administered as a 1.0 M solution in hexanes), and the reaction mixture was stirred at room temperature for 1 h. At this time, the reaction mixture was quenched with saturated aq. NaHC0 ₃ and extracted into CH2CI2. The combined organic layers were dried with MgSCh, filtered through Celite, and concentrated. The crude reaction mixture was purified via gradient column chromatography on a Teledyne-Isco Combiflash instrument, eluting with hexanes : EtOAc . Representative Products

84 % yield (isolated) . The reaction was run according to the general procedure using 4-phenyl-l-butene and BEt ₃ ; the product was isolated via gradient column chromatography on silica gel as a white solid. ¹⁹ F NMR (377 MHz, CDC1 ₃ ) : 57.59 (4F, t, J = 8.5

Hz, becomes s in ¹⁹ F{ ¹ H} spectrum); ¾ NMR (400 MHz, CDC1 ₃ ) : 9.10 (1H, d, J = 2.1 Hz), 8.44 (1H, d, J = 8.5 Hz), 7.80 (1H, d, J = 8.5 Hz), 7.34-7.21 (5H, m) , 4.60-4.54 (1H, m) , 4.46-4.34 (1H, m, becomes dd, J = 13.7, 5.3 Hz in ¹ H{ ¹⁹ F} spectrum), 4.33-4.20 (1H, m, becomes dd, J = 13.7, 7.2 Hz in ¹ H{ ¹⁹ F} spectrum), 4.00 (3H, s), 3.00 (1H, ddd, J = 14.0, 9.2, 4.5 Hz), 2.87-2.80 (1H, m) ,

2.52-2.44 (1H, m) , 2.18-2.08 (1H, m) ; “C^H} NMR (101 MHz,

CDCls) : 172.6 (quint, J = 31.7 Hz), 164.3, 148.6 (m) , 140.2,

139.6, 128.53, 128.49, 127.9, 126.3, 121.1 (quint, J = 4.8 Hz), 81.6 (quint, J = 18.7 Hz), 56.5 (quint, J = 5.2 Hz), 52.8, 39.2,

32.3.

70% yield (isolated) . The reaction was run according to the general procedure using phenylacetylene and BEt3; the product was isolated via gradient column chromatography on silica gel as a white solid. ¹⁹ F NMR (282 MHz, CD ₃ CN) : 71.26 (4F, d, J = 8.4 Hz, becomes s in ¹⁹ F{ ¹ H} spectrum); ^X H NMR (400 MHz, CDCI3) : 8.01 (1H, dm, J = 2.2 Hz), 7.86 (1H, dd, J = 8.9, 2.2 Hz), 7.81 (1H, dm, J = 8.9 Hz), 7.43-7.38 (5H, m) , 7.18 (1H, quint, J = 8.4 Hz), 3.91 (3H, s) ; ¹³ C { ¹ H} NMR (101 MHz, CDC1 ₃ ) : 164.2, 161.7 (quint, J = 27.6 Hz), 148.6, 143.0 (quint, J = 28.6 Hz), 139.8 (quint, J = 7.8 Hz), 136.5, 129.7 (quint, J = 5.4 Hz), 129.5, 128.1, 127.9 (m) , 127.2, 123.8, 53.6.

Example 12 : Representative Procedure for Synthesis of

Difluoro (aryl) (trifluoromethyl) -X ⁴ -sulfane Compound and

Application as Putative Nucleophilic Fluorinating Reagent

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N ₂ atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl (trifluoromethyl) sulfane substrate (0.46 mmol, 1.0 equiv.) in 1.5 ml MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PT E syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD ₃ CN) for ¹⁹ F NMR yield determination.

In order to remove KF and TCICA (and its byproducts) outside of the glove box, the crude reaction mixture was first filtered into a polyethylene centrifuge tube and concentrated by blowing N ₂ over it. Then, it was diluted with dry pentane, filtered into a polyethylene centrifuge tube, and concentrated by blowing N ₂ over it. The crude material consisted of mostly the aryl- SF ₄ CI product (amount quantified by ¹⁹ F NMR) and was carried forward without further purification (~0.34 mmol isolated aryl- SF2CF3 based on ¹⁹ F NMR analysis) .

A solution of the difluoro (aryl) ( trifluoromethyl) -X ⁴ -sulfane substrate (~0.34 mmol, 1.0 equiv.) in 4 mL CHCI3 was added to an oven-dried microwave vial equipped with a stir bar and sealed with a cap with septum under Ar atmosphere. Subsequently, 4- fluorobenzyl alcohol (0.04 mL, 0.37 mmol, 1.1 equiv.) was added to the vial, and the reaction mixture was stirred at room temperature. After 45 min, an aliquot was taken from the reaction mixture for ¹⁹ F NMR analysis. (Note: trifluorotoluene was added to the solution as an internal reference, but not for quantification purposes.)

Representative Products

77% yield (by ¹⁹ F NMR) . The reaction was run according to the representative procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -13.99 (2F, q, J = 17.9 Hz), -62.77 (3F, t, J = 17.9 Hz) . The reaction was run according to the representative procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -113.51 (IF, m) , -203.83 (IF, t, J =

48.1 Hz) .

Example 13: General Procedure for Synthesis of Trifluoromethyl Tetrafluoro-A6-sulfanyl Chloride d.

^► CF3SF4CI

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 18 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 32 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the disulfide substrate (0.23 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared for 19F NMR analysis.

The product (synthesized from 1- ( 4-nitrophenyl ) -2-

(trifluoromethyl) disulfide) is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN) : trans isomer: +102.88 (4F, q, J = 22.2 Hz), -65.39 (3F, quint, J = 22.2 Hz); cis-isomer: +134.48 (IF, qq, J = 146.6, 9.1 Hz),

+83.55 (2F, ddq, J = 146.6, 102.9, 19.7 Hz), +40.83 (IF, dtq, J = 146.6, 102.9, 22.8 Hz), -65.95 (3F, dtd, J = 22.8, 19.7, 9.1

Hz). cis:trans ratio: 3:1.

Example 14: General Procedure for Synthesis of Diaryl

Tetrafluoro-A6-tellane Compounds cond.

Ar-Te-Ar - _► Ar ₂ TeF ₄

Trichloroisocyanuric acid (0.319 g, 1.4 mmol, 3.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.319 g, 5.5 mmol, 12 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the diaryl monotelluride substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.1 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 20 h) . Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

Representative Product

39% trans and 6% cis observed by 19F NMR. The products are consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN) : trans-isomer: -58.11 (4F, s); cis-isomer: -37.07 (2F, t, J = 87.5 Hz), -77.29 (2F, t, J = 87.5 Hz). Example 15: General Procedure for Synthesis of Aryl Tetrafluoro- lb-sulfanyl Chloride Compounds cond.

Ar-SCI - ► Ar— SF ₄ CI

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 18 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the sulfenyl chloride substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

Representative Product

68% yield by 19F NMR. The product (synthesized from 4- nitrobenzenesulfenyl chloride) is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN) : +135.02 ( 4F, s) . Example 16: General Procedure for Synthesis of Aryl Tetrafluoro- X6-sulfanyl Chloride Compounds cond.

Ar-SMe - ► Ar-SF ₄ CI Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 18 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl methyl sulfide substrate (0.46 mmol, 1.0 equiv.) in 1.5 mL MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

Representative Product

The product is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN) : +136.61 (4F, s) .

Example 17: General Procedure for Synthesis of

Difluoro (aryl) (trifluoromethyl) -A4-selane Compounds

.Se cond. ,F

Ar CF ₃ Ar' ^Se 'CF ₃

Trichloroisocyanuric acid (0.958 g, 4.1 mmol, 9.0 equiv. ) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.425 g, 7.3 mmol, 16 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl (trifluoromethyl) selane substrate (0.46 mmol, 1.0 equiv.) in 1.5 ml MeCN was added to the vial, followed by a solution of trifluoroacetic acid (1.8 microliters, 0.02 mmol, 0.05 equiv.) in 0.5 mL MeCN. The reaction mixture was stirred vigorously at room temperature overnight (ca. 14 h) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

Representative Product

71% yield (by 19F NMR) . The reaction was run according to the general procedure. 19F NMR (282 MHz, CD3CN) : -58.30 (3F, t, J = 12.2 Hz), -73.21 (4F, t, J = 12.2 Hz). Example 18: General Procedure for Synthesis of

Tetrafluoro (aryl) - l 5-iodane Compounds cond.

Ar— I Ar— IF ₄

Trichloroisocyanuric acid (0.350 g, 1.5 mmol, 4.0 equiv.) was added to an oven-dried microwave vial equipped with a stir bar; the vessel was then transported inside a glove box under N2 atmosphere. Spray-dried (or crushed and rigorously dried) potassium fluoride (0.131 g, 2.3 mmol, 6.0 equiv.) was added to the reaction vessel, which was then sealed with a cap with septum using a crimper. The closed vial was removed from the glove box. Under Ar atmosphere, a solution of the aryl iodide substrate (0.38 mmol, 1.0 equiv.) in 4.0 mL MeCN was added to the vial. The reaction mixture was stirred vigorously at room temperature for ca. 48 h. Substrates with limited solubility in MeCN were introduced to the reaction mixture as solids in the glove box (and possibly diluted 2-fold to assist stirring) . Upon reaction completion, an aliquot of the reaction mixture was passed through a PTFE syringe filter, and an NMR sample was prepared with 0.4 mL of the filtered aliquot + 0.1 mL internal standard solution (made immediately prior to use with x g of trifluorotoluene in y mL CD3CN) for 19F NMR yield determination.

Representative Product

85% yield by 19F NMR. The product is consistent with previously reported characterization data. 19F NMR (282 MHz, CD3CN) : - 25.86 ( 4F, br s) , -104.29 to -104.46 (IF, m) .

The following compounds were synthesized using the reaction conditions described above:

Compound 101.

The reaction was run according to the general procedure, and the product was converted to the more stable aryl tetrafluoro-l ⁶ - sulfanyl alkene 232 to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +134.63 (4F, s) . Compound. 102.

The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene 227 to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +135.95 (4F, s) .

Compound 103 The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene 111 to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +137.43 (4F, s) .

Compound 104.

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +136.81 (4F, s) . Compound 105.

run according to the general procedure. ¹⁹ F CN) : +136.73 (4F, s) , -58.56 (3F, s) .

The reaction was run according to the general procedure. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +134.96 (4F, s) , +81.54 (IF, quint, J = 148.5 Hz), +61.86 ( 4F, d, J = 148.5 Hz).

Compound 107.

The reaction was run according to the general procedure, and the product was converted to the more stable aryl tetrafluoro-l ⁶ - sulfanyl alkane 228 to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +123.52 (4F, s) .

Compound 108.

The reaction was run according to the general procedure. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +120.59 (4F, s) . Coiapound 111 .

The reaction was run according to the general procedure using AgF in a copper vessel; the product was isolated via gradient column chromatography on silica gel in 77% yield (46 mg, 0.18 mmol) as a white solid. ¹⁹ F NMR (377 MHz, CDCI3) : 84.32 (IF, quint, J = 150.6 Hz), 63.62 (4F, d, J = 150.6 Hz); ¾ NMR (400

MHz, CDCI3) : 7.78 (2H, dm, J = 9.1 Hz), 7.20 (2H, d, J = 9.1

Hz), 2.33 (3H, s); ^C^H} NMR (101 MHz, CDC1 ₃ ) : 168.7, 152.5,

150.9 (quint, J = 18.0 Hz), 127.5 (quint, J = 4.8 Hz), 121.8, 21.0.

Compound 201 .

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +136.61 (4F, s) . Compound 202

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +136.08 (4F, s), -111.34 (IF, m) .

Compound 203.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +137.65 (4F, s), -108.21 (IF, m) .

Compound 204.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +136.75 (4F, s) .

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +136.59 (4F, s) .

Compound 206.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +135.61 (4F, s) , -63.21 (3F, s) .

Compound 207.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +135.02 (4F, s) .

Compound 214.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +140.30 (4F, d, J = 24.5 Hz), - 110.04 (IF, m) .

Compound 215. The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +137.64 (4F, s) .

Compound 216. The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +124.66 (4F, s) .

Compound 217.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +123.42 (4F, s) .

Compound 219. The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +119.06 (4F, s).

Compound 220.

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +118.97 (4F, s).

Compound 222.

The reaction was run according to the general procedure; the product was unstable toward isolation and characterized by ¹⁹ F NMR. ¹⁹ F NMR (471 MHz, CD ₃ CN) : +63.46 (2F, d, J = 75.6 Hz), -

56.31 (IF, t, J = 75.6 Hz) .

Compound 223. The reaction was run according to the general procedure; the product was unstable toward isolation and characterized by ¹⁹ F NMR. ¹⁹ F NMR (377 MHz, CD ₃ CN) : +53.58 (2F, d, J = 102.2 Hz), -

67.65 (IF, t, J = 102.2 Hz).

Compound 224. The reaction was run according to the general procedure; the product was unstable toward isolation and characterized by ¹⁹ F

NMR. The product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CD ₃ CN) : -25.51 (3F, br s) . Compound 226.

The reaction was run according to the general procedure using AgF in a copper vessel followed by the LiOH workup modification; the product was isolated via gradient column chromatography on silica gel in 68% yield (21 mg, 0.10 mmol) as a white solid. The product is consistent with previously reported characterization data. ¹⁹ F NMR (377 MHz, CDC1 ₃ ) : 86.05 (IF, quint, J = 150.0 Hz), 64.32 ( 4F, d, J = 150.0 Hz); ¾ NMR (400 MHz, CDC1 ₃ ) : 7.65 (2H, dm, J = 9.1 Hz), 6.86 (2H, dm, J = 9.1 Hz), 5.17 (1H, br s) . Compound 227.

The reaction was run according to the general procedure using AgF in a copper vessel; the product was isolated via gradient column chromatography on silica gel in 57% yield (20 mg, 0.07 mmol) as a colorless oil. ¹⁹ F NMR (471 MHz, CDCI3) : 83.35 (IF, quint, J = 150.4 Hz), 62.79 (4F, d, J = 150.4 Hz); ¾ NMR (500 MHz, CDCI3) : 8.43 (1H, m) , 8.20 (1H, d, J = 7.8 Hz), 7.94 (1H, m) , 7.56 (1H, t, J = 8.0 Hz), 4.43 (2H, q, J = 7.1 Hz), 1.42 (3H, t, J = 7.1 Hz); ^C^H} NMR (126 MHz, CDC1 ₃ ) : 164.8, 153.9 (quint, J = 18.2 Hz), 132.5, 131.5, 130.0 (quint, J = 4.6 Hz), 128.9, 127.2 (quint, J= 4.6 Hz), 61.8, 14.3. Compound 228.

The reaction was run according to the general procedure using 4- phenyl-l-butene and BEt3; the product was isolated via gradient column chromatography on silica gel in 84% yield (25 mg, 0.06 mmol) as a white solid. Although this product proved stable toward column chromatography, note that it degraded after a few days in CDCI3 solution in the NMR tube. ¹⁹ F NMR (377 MHz,

CDCI3) : 57.59 (4F, t, J = 8.5 Hz, becomes s in ¹⁹ F{ ¹ H} spectrum); ¹ H NMR (400 MHz, CDC1 ₃ ) : 9.10 (1H, d, J = 2.1 Hz), 8.44 (1H, d, J = 8.5 Hz), 7.80 (1H, d, J = 8.5 Hz), 7.34-7.21 (5H, m) , 4.60-

4.54 (1H, m) , 4.46-4.34 (1H, m, becomes dd, J = 13.7, 5.3 Hz in ¹ H{ ¹⁹ F} spectrum), 4.33-4.20 (1H, m, becomes dd, J = 13.7, 7.2 Hz in ¹ H{ ¹⁹ F} spectrum), 4.00 (3H, s) , 3.00 (1H, ddd, J = 14.0, 9.2,

4.5 Hz), 2.87-2.80 (1H, m) , 2.52-2.44 (1H, m) , 2.18-2.08 (1H, m) ; ¹³ C { ¾} NMR (101 MHz, CDC1 ₃ ) : 172.6 (quint, J = 31.7 Hz),

164.3, 148.6 (m) , 140.2, 139.6, 128.53, 128.49, 127.9, 126.3,

121.1 (quint, J = 4.8 Hz), 81.6 (quint, J = 18.7 Hz), 56.5

(quint, J = 5.2 Hz), 52.8, 39.2, 32.3.

Compound 232.

The reaction was run according to the general procedure using phenylacetylene and BEt3; the product was isolated via gradient column chromatography on silica gel in 70% yield (40 mg, 0.09 mmol) as a white solid. Although this product proved stable toward column chromatography, note that it degraded after a few days in CDCI3 solution in the NMR tube. ¹⁹ F NMR (282 MHz, CD3CN) : 71.26 (4F, d, J = 8.4 Hz, becomes s in ¹⁹ F{ ¹ H} spectrum); ¾ NMR (400 MHz, CDC1 ₃ ) : 8.01 (1H, dm, J = 2.2 Hz), 7.86 (1H, dd, J = 8.9, 2.2 Hz), 7.81 (1H, dm, J = 8.9 Hz), 7.43-7.38 (5H, m) , 7.18 (1H, quint, J = 8.4 Hz), 3.91 (3H, s) ; ¹³ 0{¾} NMR (101 MHz, CDCI3) : 164.2, 161.7 (quint, J = 27.6 Hz), 148.6, 143.0

(quint, J = 28.6 Hz), 139.8 (quint, J = 7.8 Hz), 136.5, 129.7 (quint, J = 5.4 Hz), 129.5, 128.1, 127.9 (m) , 127.2, 123.8,

53.6.

Compound. 233

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : trans-isomer : +143.21 (4F, t, J

= 27.6 Hz), -135.35 (2F, m) , -148.85 (IF, m) , -161.05 (2F, m) ; cis-isomer: +153.07 (IF, q, J = 158.3 Hz), +122.77 (2F, ddd, J = 158.3, 95.1, 78.2 Hz), +79.21 (IF, dtt, J = 158.3, 95.1, 20.9 Hz), -135.35 (2F, m) , -148.85 (IF, m) , -161.05 (2F, m) . transicis ratio: 1.5:1.

Compound 234

The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +136.39 (4F, s) . Compound 235

The reaction was run according to the general procedure using 4.0 equiv. AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 81% yield (23 mg, 0.07 mmol) as a yellow oil. ¹⁹ F NMR (471 MHz, CDCI3) : 83.53 (IF, quint, J = 150.8 Hz), 63.08 (4F, d, J = 150.8 Hz); ¹ H NMR (500 MHz, CDCI3) : 8.22-8.20 (2H, m) , 7.70-7.66 (3H, m) , 7.56- 7.53 (3H, m) , 7.44-7.43 (1H, m) ; ¹³ C{ ^X H} NMR (126 MHz, CDC1 ₃ ) : 164.6, 154.3 (quint, J = 18.2 Hz), 150.5, 134.1, 130.3, 129.5,

128.7, 125.3, 123.4 (quint, J = 4.6 Hz), 120.1 (quint, J = 4.6 Hz). D _max (ATR-IR) : 1743 cm ¹ . HRMS (ESI-TOF) : calc'd for

Ci3H ₉ F ₅ Na02S [M+Na] ⁺ : 347.0136, found: 347.0131.

Compound 236 The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +135.78.

Compound 237

The reaction was run according to the general procedure using AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 57% yield (18 mg, 0.06 mmol) as a white solid; m.p. 116.4-117.3 °C. ¹⁹ F NMR (377 MHz,

CDCla) : 83.11 (IF, quint, J = 150.4 Hz), 62.64 (4F, d, J = 150.4 Hz); 4i NMR (400 MHz, CDC1 ₃ ) : 7.90-7.85 (4H, m) , 7.82-7.79 (2H, m) , 7.66-7.62 (1H, tm, J = 7.4 Hz), 7.54-7.49 (2H, m) ; “C^H}

NMR (101 MHz, CDC1 ₃ ) : 194.9, 156.2 (quint, J = 18.1 Hz), 140.3, 136.5, 133.3, 130.09, 130.08, 128.6, 126.1 (quint, J = 4.7 Hz), □max (ATR-IR) : 1653 crrr ¹ . HRMS (El): calculated for Ci ₃ HgF50S

[M] ⁺ : 308.0289, found: 308.0282. Compound 238

The reaction was run according to the general procedure, and the product was converted to the more stable pentafluorosulfanyl arene to obtain complete characterization data. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +137.77 (4F, s) .

The reaction was run according to the general procedure using AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 63% yield (21.3 mg, 0.09 mmol) as a light yellow oil. ¹⁹ F NMR (471 MHz, CDCI3) : 84.59

(IF, quint, J = 150.8 Hz), 63.67 (4F, quint, J = 150.8 Hz); ^X H

NMR (500 MHz, CDC1 ₃ ) : 7.74 (2H, d, J = 9.0 Hz), 7.08 (2H, d, J = 9.0 Hz) . The product is consistent with previously reported characterization data.

Compound 240

PhthN

The reaction was run according to the general procedure using 4.0 equiv. AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 80% yield (6.9 mg, 0.02 mmol) as a white solid; m.p. 217.2-219.0 °C. ¹⁹ F NMR

(471 MHz, CDCI ₃ ) : 83.79 (IF, quint, J= 150.5 Hz), 63.14 (4F, d, J = 150.5 Hz); ¾ NMR (500 MHz, CDC1 ₃ ) : 7.99 (2H, dd, J = 5.4,

3.1 Hz), 7.90 (2H, d, J = 9.1 Hz), 7.84 (2H, dd, J = 5.4, 3.1

Hz), 7.65 (2H, d, J = 9.1 Hz); “C^H} NMR (126 MHz, CDC1 ₃ ) :

166.6, 152.5 (quint, J = 18.2 Hz), 134.8, 134.6, 131.4, 126.9 (quint, J = 4.5 Hz), 126.1, 124.1. D^ _x (ATR-IR) : 1720, 1711, 1702 cm ¹ . HRMS (ESI-TOF) : calc'd for C ₁₄ H ₉ F ₅ NO ₂ S [M+H] ⁺ :

350.0269, found: 350.0268. The product is consistent with previously reported characterization data.

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : +137.59 (4F, s) .

Compound 243

The reaction was run according to the general procedure. 19p NMR (282 MHz, CD ₃ CN) : +137.13 (4F, s) .

Compound 244

The reaction was run according to the general procedure using AgF in a PFA vessel; the product was isolated via gradient column chromatography on silica gel in 59% yield (20 mg, 0.06 mmol) as a white solid; m.p. 82.8-84.8 °C. ¹⁹ F NMR (471 MHz,

CDC1 ₃ ) : +84.60 (IF, quint, J = 150.2 Hz), +63.24 (4F, d, J =

150.2 Hz); ¾ NMR (500 MHz, CDC1 ₃ ) : 7.83 (2H, dm, J = 8.6 Hz), 7.62 (2H, br d, J = 8.6 Hz), 7.52 (2H, dm, J = 8.6 Hz), 7.45 (2H, dm, J = 8.6 Hz); “C^H} NMR (126 MHz, CDC1 ₃ ) : 153.1 (quint,

J = 17.5 Hz), 143.3, 137.5, 134.8, 129.3, 128.5, 127.1, 126.6 (quint, J= 4.6 Hz). CW _ax (ATR-IR) : 840 cm ¹ (br) , 813 cm- ¹ .

The reaction was run according to the general procedure, and the product is consistent with previously reported characterization data. Colorless oil. ¹⁹ F NMR (282 MHz, CDC1 ₃ ) : -37.11 (IF, quint, J = 150.6 Hz), -53.39 (4F, d, J = 150.6 Hz); ¾ NMR (400

MHz, CDCI3) : 7.92 (2H, d, J = 8.1 Hz), 7.83-7.78 (1H, m) , 7.75- 7.70 (2H, m) ; ¹³ ΰ{¾} NMR (101 MHz, CDC1 ₃ ) : 142.2-141.9 (m) ,

135.4, 131.4 (quint, J = 1.5 Hz), 130.3 (quint, J = 2.2 Hz) . C _c (ATR-IR) : 655 cm- ¹ (br) . HRMS (El): calc'd for C ₆ H ₅ F ₅ Te [M] ⁺ :

301.9374, found: 301.9374.

Compound 246

The reaction was run according to the general procedure. Clear solid; m.p. 75.4-76.3 °C. ¹⁹ F NMR (282 MHz, CDCI3) : -37.25 (IF quint, J = 151.7 Hz), -52.22 (4F, d, J = 151.7 Hz); ¾ NMR (400 MHz, CDC1 ₃ ) : 7.88 (2H, d, J = 8.7 Hz), 7.71 (2H, dquint, J = 8.7, 1.5 Hz); ¹³ C{ ^X H} NMR (126 MHz, CDC1 ₃ ) : 142.6, 139.6 (quintd, J = 8.5, 2.6 Hz), 131.53 (m) , 131.47. P _ma* (ATR-IR) : 656 cirr ¹

(br) . HRMS (El) : calc'd for C ₆ H ₄ ClF ₅ Te [M] ⁺ : 335.8978, found: 335.8967. Compound 247

The reaction was run according to the general procedure. Colorless oil. ¹⁹ F NMR (377 MHz, CDCI3) : -37.42 (IF, quint, J = 152.0 Hz), -51.96 (4F, d, J = 152.0 Hz), -57.61 (3F, s) ; ¾ NMR (400 MHz, CDCI3) : 8.01 (2H, d, J = 8.9 Hz), 7.55 (2H, dm, J =

8.9 Hz); ¹³ C{^H} NMR (101 MHz, CDC1 ₃ ) : 154.1 (q, J = 2.2 Hz),

138.7 (quintd, J = 9.2, 2.9 Hz), 132.6 (quint, J = 2.5 Hz),

133.1 (dquint, J = 9.7, 2.5 Hz), 118.8 (dquint, J = 23.1, 1.7 Hz) . [U _max (ATR-IR) : 666 cm ^-1 (br) . HRMS (El) : calc'd for C ₆ H ₄ F ₆ Te [M] ⁺ : 319.9274, found: 319.9273.

Compound 249

The reaction was run according to the general procedure. Waxy white solid. ¹⁹ F NMR (377 MHz, CDCI3) : -37.27 (IF, quint, J =

151.8 Hz), -52.28 (4F, d, J = 151.8 Hz); ^X H NMR (400 MHz, CDC1 ₃ ) : 7.87 (2H, dquint, J = 8.8, 1.5 Hz), 7.79 (2H, d, J = 8.8 Hz); ^C^H} NMR (101 MHz, CDC1 ₃ ) : 140.3 (quintd, J = 8.8, 2.9 Hz), 134.4 (m) , 131.5 (quint, J= 2.3 Hz), 131.1. D^ _x (ATR-IR) : 654 cm- ¹ (br) . HRMS (El): calc'd for C ₆ H ₄ BrF ₅ Te [M] ⁺ : 379.8473, found: 379.8453.

Compound 250

The reaction was run according to the general procedure. Note that we were unable to isolate an analytically pure sample. White solid. ¹⁹ F NMR (377 MHz, CDC1 ₃ ) : -36.49 (IF, quint, J =

150.8 Hz), -53.11 (4F, d, J = 150.8 Hz); ¾ NMR (400 MHz,

CDCI3) : 7.83 (2H, d, J = 8.8 Hz), 7.71 (2H, dquint, J= 8.8, 1.7 Hz), 1.37 ( 9H, s) . Q _nax (ATR-IR): 661 cm- ¹ (br) . HRMS (El): calc'd for Ci ₀ Hi ₃ F ₅ Te [M] ⁺ : 357.9994, found: 357.9987.

Compound 251

The reaction was run according to the general procedure. White solid; m.p. 86.2-86.9 °C. ¹⁹ F NMR (377 MHz, CD ₃ CN) : -37.57 (IF, quint, J = 148.4 Hz), -54.25 (4F, d, J = 148.4 Hz); ¾ NMR (400 MHz, CD ₃ CN) : 8.00 (2H, d, J = 8.7 Hz), 7.91 (2H, dquint, J =

8.7, 1.8 Hz), 4.10-4.02 (2H, m) , 3.80-3.71 (2H, m) , 1.63 (3H, s); ¹³ C { ² H} NMR (101 MHz, CD ₃ CN) : 153.5, 141.2 (quintd, J = 5.9,

2.9 Hz), 131.2 (quint, J = 2.2 Hz), 129.9 (quint, J = 1.5 Hz), 108.5, 65.6, 27.4. O _nax (ATR-IR): 661 cm- ¹ (br) . HRMS (El): calc'd for CgHeC^FsTe [M] ⁺ : 372.9501, found: 372.9502. Compound 252

The reaction was run according to the general procedure.

Colorless oil. ¹⁹ F NMR (471 MHz, CD ₃ CN) : -38.42 (IF, quint, J =

149.4 Hz), -53.93 (4F, d, J = 149.4 Hz), -106.22 (IF, m) ; ^X H NMR (500 MHz, CD ₃ CN) : 7.93-7.84 (3H, m) , 7.72-7.69 (3H, m) ; ¹³ C{ ¹ H} NMR (126 MHz, CD ₃ CN) : 164.0 (dquint, J = 255.1, 2.7 Hz), 141.9- 141.5 (m) , 134.7 (dquint, J = 8.2, 1.8 Hz), 127.7-127.6 (m) ,

124.9 (d, J = 20.9 Hz), 118.9 (dm, J = 26.3) . D^ _x (ATR-IR) : 672 c ^-1 (br) .

Compound 253

The reaction was run according to the general procedure, White solid; m.p . 127.6-128.6 °C. ¹⁹ F NMR (377 MHz, CD ₃ CN) : -37.64 (IF, quint, J = 148.3 Hz), -54.03 (4F, d, J = 148.3 Hz), -63.10 (3F, s); ^X H NMR (400 MHz, CD ₃ CN) : 8.16-8.10 (4H, m) , 7.92 (2H, dm, J = 8.4 Hz), 7.87 (2H, dm, J = 8.4 Hz). D _max (ATR-IR) : 665 cm ^-1 (br) . Compound 254

The reaction was run according to the general procedure. White solid; m.p. 94.2-96.4 °C. ¹⁹ F NMR (377 MHz, CD ₃ CN) : -38.28 (IF, quint, J = 148.6 Hz), -54.16 (4F, d, J = 148.6 Hz); ¾ NMR (400 MHz, CD ₃ CN) : 8.16 (2H, br d, J = 8.6 Hz), 8.10 (2H, dquint, J = 8.6, 1.7 Hz), 7.84-7.81 (2H, m) , 7.73 (1H, tm, J = 7.5 Hz),

7.61-7.56 (2H, m) ; ¹³ C {’H} NMR (101 MHz, CD ₃ CN) : 195.3, 145.4,

144.5-144.2 (m) , 136.9, 134.7, 133.3 (quint, J = 1.5 Hz), 131.5 (quint, J = 2.2 Hz), 131.07, 129.7. C (ATR-IR) : 1664 cm ^-1 , 662 cm- ¹ (br) . HRMS (El) : calc'd for Ci ₃ H ₉ F ₅ OTe [M] ⁺ : 405.9630, found: 405.9632.

Compound 255

The reaction was run according to the general procedure. Light yellow oil. ¹⁹ F NMR (377 MHz, CD ₃ CN) : -54.17 (3F, quint, J = 21.8 Hz), -68.75 (4F, q, J = 21.8 Hz); ^X H NMR (400 MHz, CD ₃ CN) :

8.03 (2H, dm, J = 8.2 Hz), 7.91 (1H, tm, J = 7.5 Hz), 7.86-7.80

(2H, m) ; ¹³ C{ ^X H} NMR (101 MHz, CD ₃ CN) : 142.7 (quint, J = 8.6 Hz), 137.0, 132.7, 131.1 (quint, J = 2.2 Hz) . Note: ¹³ C NMR signal for "CF ₃ " was not resolved. (ATR-IR) : 625 cirr ¹ (br) .

Compound 256

The reaction was run according to the general procedure. ¹ H NMR (400 MHz, CD ₃ CN) : d = 8.72 (1H, d, J= 7.8 Hz), 8.06 (1H, d, J= 7.7 Hz), 7.93 (1H, t, J = 7.8 Hz), 7.85 (1H, t, J = 7.8 Hz); ¹³ C{ ¹ H} NMR (101 MHz, CD ₃ CN) : d = 140.3, 136.6 - 136.5 (m) , 134.6 (t, J= 1.8 Hz), 129.8 (q, J = 32.6 Hz), 129.00 (q, J= 5.4 Hz), 125.2 (q, J= 273.7 Hz), 124.3 (tq, J= 14.3, 1.7 Hz); ¹⁹ F NMR

(376 MHz, CD ₃ CN) : d = -60.36 (3F, s) , -161.65 (2F, s) . Compound 257

The reaction was run according to the general procedure . ¹ H NMR (400 MHz, CD ₃ CN) : d = 8.75 (1H, br dd, J= 8.7, 5.1 Hz), 7.80

(1H, br d, J= 8.7 Hz), 7.56 (1H, br t, J = 7.3 Hz); ^C^H} NMR

(101 MHz, CDsCN) : d = 165.1 (d, J= 256.2 Hz), 143.5 (d,

J = 9.4 Hz), 133.1 (qd, J= 33.7, 8.9 Hz), 123.5 (d,

J = 22.1 Hz), 123.0 (qd, J = 273.9, 2.3 Hz), 119.7 - 119.1 (m), 117.7 (dq, J = 21. Q, 5.5 Hz); ¹⁹ F NMR (376 MHz, CD ₃ CN) : d =

-60.82 (3F, s), -103.17 (IF, s), -159.84 (2F, s).

Compound 258

The reaction was run according to the general procedure. ¾ NMR (500 MHz, CDsCN) : d = 8.67 (1H, d, J = 8.5 Hz), 8.05 (1H, s.), 7.84 (1H, d, J = 8.5 Hz); ¹³ C { ¾} NMR (126 MHz, CD ₃ CN) : d = 141.9, 140.6, 136.5, 131.8 (q, J = 33.2 Hz), 129.6 (q

J = 5.4 Hz), 123.2 (q, J = 274.2 Hz), 122.2 (tm, J = 14.7 Hz) ; ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -60.77 (3F, s) , -160.27 (2F, s) .

Compound 259

The reaction was run according to the general procedure. ¾ NMR (500 MHz, CD ₃ CN) : d = 8.58 8.4 Hz), 8.20 (1H, s) , 8.00 (1H, d, J = 8.5 Hz. MR (126 MHz, CD ₃ CN) : d = 141.7, 139.5, 132.3 (q, J = 5.3 Hz), 131.6 (q, J = 33.1 Hz), 128.7 (t, J = 2.1 Hz), 123.0 (q, J = 274.3 Hz), 122.9 - 122.6 (m) ; ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -60.70 (3F, s) , -160.35 (2F, s) . Compound 260

The reaction was run according to the general procedure. ¹ H NMR (400 MHz, CDsCN) : d = 8.80 (1H, d, J = 8.2 Hz), 8.53 (1H, s) ,

8.37 (1H, d, J = 8.2 Hz), 4.42 (2H, q, J = 7.0 Hz), 1.39 (3H, t, J= 7.1 Hz); ¹³ C{¾} NMR (101 MHz, CD ₃ CN) : d = 164.6, 140.7,

136.9, 136.0, 130.4 (q, J = 33.2 Hz 129.4 (q, J = 5.3 Hz) ,

127.4 (t, J = 13.9 Hz) , 123.5 (q J = 273.8 Hz) , 63.2, 14.4;

¹⁹ F NMR (376 MHz, CD ₃ CN) : d = -60.62 (3F, s) , -161.25 (2F, s) . Compound 261

The reaction was run according to the general procedure. ¹ H NMR (500 MHz, CD ₃ CN) : d = 8.93 (1H, br d, J = 8.6 Hz), 8.73 (1H, br s), 8.59 (1H, br d, J = 8.5 Hz); ¹³ C{ ^X H} NMR (126 MHz, CD ₃ CN) : d = 150.8, 141.9, 131.7 (q, J= 34.1 Hz), 131.3, 128.3 (t, J = 14.4 Hz), 124.5 (q, J= 5.5 Hz), 122.9 (q, J= 274.3 Hz); ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -60.88 (3F, s) , -160.30 (2F, s) . Compound 262

The reaction was run according to the general procedure. ¹ H NMR (500 MHz, CDsCN) : d = 8.16 (1H, d, J= 8.2 Hz), 7.95 (1H, d, J= 7.8 Hz), 7.87 (1H, t, J = 8.2 Hz); ^! ¾{¾} NMR (126 MHz,

CDsCN ) : 6 = 139.7, 136.5, 134.6, 133.0 (q, J = 32.3 Hz), 130.2

(t, J = 14.3 Hz), 127.5 (q, J = 5.7 Hz), 123.6 (q,

J= 274.3 Hz); ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -60.10 (3F, s) ,

-163.36 (2F, s) . Compound 263

The reaction was run according to the general procedure. ¹ H NMR (500 MHz, CDsCN) : d = 8.33 (1H, d, J= 7.8 Hz), 8.22 (1H, d,

J = 7.9 Hz), 8.00 (1H, t, J = 7.9 Hz), 4.03 (3H, s); ¹³ 0{¾} NMR (126 MHz, CDsCN ) : d = 166.6, 135.5, 135.2, 134.8, 132.2 (q, J= 5.6 Hz), 131.9 (q, J= 32.0 Hz), 124.1 (q, J = 274.3 Hz),

123.4 (q, J= 14.0 Hz), 54.4; ¹⁹ F NMR (471 MHz, CD ₃ CN) : d =

-59.23 (3F, s), -159.98 (2F, s) .

Compound 264

The reaction was run according to the general procedure. ¹ H NMR (500 MHz, CDsCN) : d = 8.46 (1H, dd, J= 8.0, 1.8 Hz), 7.82 (1H, t, J= 8.0 Hz), 7.72 (1H, d, J= 8.5 Hz), 7.56 (1H, t, J= 7.8 Hz); ^C^H} NMR (126 MHz, CD ₃ CN) : d = 146.4 (q,

J = 1.8 Hz) , 137.9, 136.6 130.5, 123.2 (t, J= 13.8 Hz), 121.41

(q, J = 259.8 Hz), 121.40 (q, J= 1.9 Hz); ¹⁹ F NMR (471 MHz,

CDaCN) : d = -57.60 (3F, s) , -166.40 (2F, s) .

Compound 265

The reaction was run according to the general procedure. ¹ H NMR (500 MHz, CDaCN) : d = 7.80 (1H, t, J = 7.7 Hz), 7.37 (2H, br s) ; ¹³ C { ^! H} NMR (126 MHz, CD ₃ CN) : d = 160.0 (dd, J= 253.9, 4.6 Hz),

138.7 (dd, J= 11.2, 8.9 Hz), 113.5 - 113.2 ( ) , 108.4 - 107.6

(m) ; ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -97.43 (2F, br . s) , -165.78

(2F, s) .

Compound 266

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : d = -124.10 to -124.65 (2F, m) , -145.92 (IF, tt, J = 19.9, 5.1 Hz) -158.21 to -158.66 (2F, m) , -162.08 (2F, s) .

Compound 267

The reaction was run according to the general procedure . ¾ NMR (500 MHz, CDsCN) : d = 8.37 (1H, dt, J = 9.0, 4.6 Hz), 7.34 (1H, td, J = 8.9, 2.8 Hz), 7.20 (1H, td, J = 8.6, 2.7 Hz); 4ϊ{ ¹⁹ H} NMR (500 MHz, CDsCN) : d = 8.37 (1H, d, J = 8.9 Hz), 7.34 (1H, d, J = 2.8 Hz), 7.20 (1H, td, J = 9.0, 2.8 Hz); ^C^Hl NMR

(126 MHz, CDsCN) : d = 167.0 (ddt, J = 256.1, 12.0, 1.9 Hz),

160.4 (dd, J = 253.9, 13.3 Hz), 115.5 (dd, J = 23.0, 3.4 Hz),

112.2 (dtd, J = 23.3, 15.2, 4.5 Hz), 106.3 (t, J = 26.8 Hz); ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -94.80 (IF, d, J = 11.4 Hz), -101.28 (IF, dt, J = 11.1, 4.3 Hz), -165.09 (2F, s) .

Compound 268

The reaction was run according to the general procedure. ¹ H NMR (400 MHz, CDsCN) : d = 8.47 (1H, dd, J = 8.9, 5.6 Hz), 7.64 (1H, dd, J = 8.6, 2.8 Hz), 7.28 (1H, td, J = 8.5, 2.8 Hz); ¹³ C { ¹ H } NMR

(101 MHz, CDaCN) : d = 160.0 (dt, J = 256.6, 1.7 Hz), 140.7 (d,

J = 10.0 Hz), 138.6 (d, J = 11.5 Hz), 127.6 (td, J = 14.6,

4.0 Hz), 118.8 (t, J = 26.7 Hz), 118.3 (t, J = 22.7 Hz); ¹⁹ F NMR (376 MHz, CD ₃ CN) : d = -103.50 (IF, tq, J = 9.3, 4.8 Hz), -164.37 (2F, d, J = 4.2 Hz); ¹⁹ F{ ^X H } NMR (376 MHz, CD ₃ CN) : d = -103.50 (IF, t, J = 4.5 Hz), -164.37 (2F, d, J = 3.7 Hz).

Compound 269

The reaction was run according to the general procedure. ^X H NMR (400 MHz, CD ₃ CN) : d = 8.47 (1H, dd, J = 8.9, 5.5 Hz), 7.78 (1H, dd, J = 8.8, 2.7 Hz), 7.36 - 7.25 (1H, m) ; ¹³ C { ¾} NMR (101 MHz,

CD ₃ CN) : d = 165.5 (dt, J= 257.4, 1.7 Hz), 141.1 (d,

J = 9.6 Hz), 130.7 (td, J = 14.7, 4.0 Hz), 128.5 (d, J= 10.4 Hz), 122.0 (t, J - 26.3 Hz), 118.7 (t, J= 22.7 Hz);

¹⁹ F NMR (376 MHz, CD ₃ CN) : d = -103.74 (IF, br s) , -163.35 (2F, br s) .

Compound 270

The reaction was run according to the general procedure. ¹ H NMR

(400 MHz, CDaCN) : d = 8.32 (1H, dd, J= 8.9, 5.5 Hz), 7.34 (1H, dd, J= 9.8, 3.0 Hz), 7.12 (1H, td, J= 8.6, 3.1 Hz), 2.74 (3H, s); ¹³ C{ ^X H} NMR (101 MHz, CD ₃ CN) : d = 165.7 (dt, J = 252.4,

1.9 Hz), 144.4 (d, J= 9.5 Hz), 139.6 (d, J= 9.5 Hz), 128.5 (td, J= 13.6, 3.0 Hz), 118.9 (t, J = 23.1 Hz), 116.8 (t, J= 22.8 Hz), 25.1; ¹⁹ F NMR (376 MHz, CD ₃ CN) : d = -106.86 (IF, tt, J= 9.9, 4.8 Hz), -168.31 (2F, d, J = 3.7 Hz); ¹⁹ F{ ^X H } NMR

(376 MHz, CDaCN): d = -106.86 (IF, t, J = 4.7 Hz), -168.32 (2F, d, J = 4.2 Hz) . Compound 271

The reaction was run according to the general procedure. ^X H NMR (500 MHz, CD ₃ CN) : d = 8.39 (1H, d, J = 8.0 Hz), 7.85 - 7.77 (2H, m) , 7.57 (1H, d, J = 7.6 Hz), 6.07 (1H, dd, J= 46.1, 6.4 Hz), 1.72 ( 3H, dd, J= 24.1, 6.4 Hz); ¹³ C{ ^X H} NMR (126 MHz, CD ₃ CN) :

141.8 (d, J = 20.9 Hz), 137.3, 134.7, 132.4, 129.4 (td,

J = 13.2, 4.3 Hz), 128.5 (d, J= 1.7 Hz), 93.8 (d,

J = 129.7 Hz), 23.5 (d, J= 25.2 Hz); ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -165.35 (2F, s), -165.58 (IF, dq, J= 47.8, 24.2 Hz). Compound 272

The reaction was run according to the general procedure. ¾ NMR (500 MHz, CD ₃ CN) : d = 8.42 (1H, d, J = 8.0 Hz), 7.85 - 7.77 (2H, m) , 7.61 (1H, br t, J = 7.5 Hz), 7.45 (2H, br t, J = 6.9 Hz), 7.17 (2H, br t, J= 8.5 Hz), 7.02 (1H, d, J = 46.1 Hz);

“C^H} NMR (126 MHz, CD ₃ CN) : d = 163.6 (dd, J = 246.6, 2.8 Hz),

139.6 (d, J= 23.1 Hz), 138.1 (d, J = 28.4 Hz), 137.6, 134.9

(dd, J = 22.2, 3.2 Hz), 134.6, 132.8 (d, J= 1.8 Hz), 130.6 (dd, J= 8.7, 5.8 Hz), 129.7 (d, J = 8.6 Hz), 116.6 (d, J= 21.9 Hz), 95.4 (d, J= 174.0 Hz); ¹⁹ F NMR (471 MHz, CD ₃ CN) : d = -113.59

(IF, br. s), -161.74 (IF, d, J = 46.2 Hz), -165.69 (2F, br. s) .

Compound 273

The reaction was run according to the general procedure. ¾ NMR (500 MHz, CD2CI2) : d = 8.16 (1H, d, J = 8.4 Hz), 7.79 (1H, dd,

J = 8.4, 2.1 Hz), 5.97 (1H, dt, J = 49.3, 3.2 Hz), 3.12 - 3.05 (1H, m) , 2.67 - 2.54 (1H, m) , 2.50 - 2.41 (1H, m) , 2.02 - 1.95

(2H, m) , 1.92 - 1.82 (1H, m) ; ^C^H} NMR (126 MHz, CD2CI2) : d = 142.1, 136.4 (d, J = 44.2 Hz), 135.3 (d, J = 17.6 Hz),

132.0, 117.0, 88.4 (d, J = 170.1 Hz), 31.4, 29.2 (d

J = 21.5 Hz), 17.4, 2.1; ¹⁹ F NMR (471 MHz, CD ₃ CN) : 5 = -156.94 to -157.21 (IF, m) , -165.33 (2F, s) .

Compound 274

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD3CN) : -13.31 (2F, qd, J = 17.9, 2.0 Hz), -63.19 (3F, t, J = 17.9 Hz), -106.82 to -106.95 (IF, m) .

Compound 275

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD3CN) : -13.15 (2F, q, J = 18.2 Hz), -62.61 (3F, t, J = 18.2 Hz), -110.66 to -110.80 (IF, m) .

Compound 276 The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -13.80 (2F, q, J = 18.0 Hz), -62.83 (3F, t, J = 18.0 Hz) .

Compound 277

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -13.30 (2F, q, J = 18.3 Hz), -62.42 (3F, t, J = 18.3 Hz) . Compound 278

s run according to the general procedure. ¹⁹ F D ₃ CN) : -11.89 (2F, q, J = 18.0 Hz), -61.74 (3F,

s run according to the general procedure. ¹⁹ F D ₃ CN) : -13.24 (2F, q, J = 18.1 Hz), -62.12 (3F,

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -13.22 (2F, q, J = 18.3 Hz), -62.11 (3F, t, J = 18.3 Hz) . Compound 281

The reaction was run according to the general procedure. ¹⁹ F

NMR (282 MHz, CD ₃ CN) : -14.10 (2F, q, J = 18.0 Hz), -62.54 (3F, t, J = 18.0 Hz) . Compound 282

The reaction was run according to the general procedure. ¹⁹ F

NMR (282 MHz, CD ₃ CN) : -4.73 (2F, q, J = 17.6 Hz), -59.43 (3F, t, J = 17.6 Hz) .

Compound 283

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -13.66 (2F, q, J = 17.9 Hz), -63.06 (3F, t, J = 17.9 Hz) .

Compound 284

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -14.06 (2F, q, J = 18.3 Hz), -62.80 (3F, t, J = 18.3 Hz) . Compound. 286

The reaction was run according to the general procedure. ¹⁹ F NMR (282 MHz, CD ₃ CN) : -14.36 (2F, q, J = 18.0 Hz), -63.62 (3F, t, J = 18.0 Hz) .