D e s c r i p t i o n

The present invention relates to the field of isomerization of alkenes.

The carbon-carbon double bond is one of the most important functional groups in molecular chemistry. However, many synthetic methods to generate alkenes are not stereoselective, furthermore for many alkenes, the E and Z isomers are difficult to separate.

Hence, there is a constant need for methods for the stereoselective synthesis of alkenes, especially of E-alkenes and therefore it is an object for the skilled person to provide such methods.

This object is met by the method of Claim 1 of the present invention. Accordingly, a method for the isomerization of alkenes is provided, comprising the step of contacting an alkene to be isomerized with a Ni(I)-compound.

Surprisingly, it has been found that by doing so for many alkenes an isomerization in good, sometimes close to quantitative yields is observed. For most applications within the present invention, at least one of the following advantages could be observed:

The reaction usually proceeds smoothly and straightforwardly The reaction can be performed at room temperature or slightly elevated temperatures

The term„isomerization“ in the sense of the present invention is to be understood in its broadest sense and may, depending on the alkene that is to be subjected to the inventive method, include the following:

Isomerization of a Z-alkene to an E-alkene (or vice versa); however, usually E-alkenes will be the predominant product.

Allylic isomerization, i.e. an isomerization with a formal l,3-H-shift

Isomerization including the migration of a double bond, e.g. along a carbon chain, over more than one carbon atom

It should be noted that according to the invented method, if the alkene to be isomerized contains more than one double bond, it is usually possible to isomerize all double bonds present in the molecule; this is insofar a preferred embodiment of the present invention.

The term“Ni(I)-compound” especially includes a chemical compound which contains nickel in the formal oxidation state (I). The present method is, however, not limited to applications or embodiments where the Ni(I)-compound is present at the beginning, according to embodiments of the present invention the Ni(I)-compound may also be formed in situ during the reaction. The Ni(I)-compound may be present in solvated form or on a solid carrier, or to put it otherwise the reaction maybe homogenous or heterogeneous.

The term“contacting” is to be understood in its broadest form and may include that the Ni(I)- compound and the alkene which is to be isomerized are reacted together with or without a solvent.

According to an embodiment of the present invention, as previously described, the Ni(I)- compound is formed in situ during the reaction from one or more suitable precursor compound(s). Suitable methods or reaction steps to form the Ni(I)-compound, either in situ or synthetically include:

1) Oxidation of Ni(0) to Ni(I)

The Ni(I)-compound can be formed from Ni(0)-precursors using suitable oxidants. Reagents found most useful include aryl halide or aryl pseudohalide compounds, because it has been found that those compounds often react smoothly with the halogen or pseudohalogen compound becoming a ligand. Most suitable reagents include aryl chlorides, especially chlorobenzene or chloro toluene. Alkyl chlorides may also serve as oxidant.

Alternatively the Ni(I)-compound can be formed using a SET (single electron transfer) process using suitable oxidants or even electrolysis.

Especially preferred Ni(0)-compounds include Ni(0)-complexes, especially Ni(cod) ₂ .

2) Comproportionation of Ni

Using suitable Ni(0) and Ni(II) precursors, the Ni(I)-compound can be formed via a comproportionation reaction. Suitable Ni(0)-compounds include Ni(0)-complexes, especially Ni(cod) _2. Suitable Ni(II)-compounds include Ni(dme)Cl ₂ or Ni(II)-carbene complexes.

3) Reduction of Ni(II)-compounds

The Ni(I)-compound can be formed from Ni(II)-precursors using suitable reductants using a SET process. According to a preferred embodiment of the present invention, the Ni(I)-compound comprises an electron-donating ligand. Especially preferred ligands are phosphines and carbenes, with carbenes especially preferred.

These Ni(I)-compounds either can be prepared as a compound or can be generated in situ using the methods shown above or via ligand-exchange reactions from other Ni(I)-precursors.

According to a preferred embodiment of the present invention the Ni(I)-compound comprises a phosphine ligand of the form PR ^X R ² R ³ with R ¹ to R ³ independently selected out of the group comprising alkyl, cycloalkyl, halogenalkyl, aryl, halogenaryl, heteroaryl.

According to a preferred embodiment of the present invention, the Ni(I)-compound comprises a carbene ligand selected from the following structures I to IV:

Structure I)

whereby R ¹ to R ³ are independently selected out of a group comprising alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, hetero arylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, formyl, carboxy- and/or carbonyl derivatives, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more Chh-groups may independently from each other substituted by -0-, -S-, -NH-, -NR ⁰ -, - SiR°R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S CO-, -CO S-, -CYl=CY2 or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH ₃ groups are understood as CH ₂ -H groups

R ⁴ to R ⁷ are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH ₂ -groups may independently from each other substituted by -O-, -S-, -NH-, -NR ⁰ -, -SiR°R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S- CO-, -CO-S-, -CYl=CY2 or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH ₃ groups are understood as CH ₂ -H groups And whereby R ¹ to R ⁷ may be so substituted that a ring is formed between R ² and R ³ , R ⁴ and R ³ , R ⁶ and R ⁷ , R ¹ and R ⁴ /R ⁵ , R ⁴ /R ⁵ and R ⁶ /R ⁷ or R ² /R ³ and R ⁶ /R ⁷

Structure II)

whereby R ¹ to R ³ are independently selected out of a group comprising alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, hetero arylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, formyl, carboxy- and/or carbonyl derivatives, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more Chh-groups may independently from each other substituted by -0-, -S-, -NH-, -NR ⁰ -, - SiR°R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S CO-, -CO S-, -CYl=CY2- or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH ₃ groups are understood as CH ₂ -H groups

R ⁴ to R ⁷ are independently selected out of a group comprising hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH ₂ -groups may independently from each other substituted by -0-, -S-, -NH-, -NR ⁰ -, -SiR°R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S- CO-, -CO-S-, -CYl=CY2 - or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH ₃ groups are understood as CH ₂ -H groups and whereby R ¹ to R ⁷ may be so substituted that a ring is formed between R ² and R ³ , R ¹ and R ² /R ³ or R ² /R ³ and R ⁷ or R ⁶ and R ⁷ or R ⁵ and R ⁶ or R ⁴ and R ⁵

Structure III)

whereby R ¹ and R ² may either be substituted or unsubstituted carbon or nitrogen, with the proviso that not R ¹ and R ² are both nitrogen, and whereby the substitution may be selected from hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy- and/or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl,

halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more CH ₂ -groups may independently from each other substituted by -O-, -S-, -NH-, -NR ⁰ -, - SiR°R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-0-, -S02-, -S CO-, -CO S-, -CYl=CY2- or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH ₃ groups are understood as CH ₂ -H groups

R ² and R ⁴ are independently selected out of a group comprising alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, halogenalkyl, aryl, arylene, halogenaryl, heteroaryl, heteroarylene, heterocycloalkylene, heterocycloalkyl, halogenheteroaryl, alkenyl, halogenalkenyl, alkinyl, halogenalkinyl, formyl, carboxy- and/or carbonyl derivatives, keto, ketoaryl, halogenketoaryl, ketoheteroaryl, ketoalkyl, halogenketoalkyl, ketoalkenyl, halogenketoalkenyl, phosphoalkyl, phosphonate, phosphate, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonate, sulphate, sulphone, amine, polyether, silylalkyl, silylalkyloxy, whereby at suitable residues one or more Chh-groups may independently from each other substituted by -0-, -S-, -NH-, -NR ⁰ -, - SiR°R ⁰⁰ -, -CO-, -COO-, -OCO-, -OCO-O-, -S02-, -S CO-, -CO S-, -CYl=CY2- or -CºC- in that way that O and/or S atoms are not directly bound to each other; terminal CH ₃ groups are understood as CH ₂ -H groups, whereby the bond between R ¹ and R ² may be a single or a double bond, and whereby R ¹ to R ⁴ may be so substituted that a ring is formed between R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ² and R ³ or R ² and R ⁴ _.

IV)

whereby R ³ und R ⁴ are defined as in Structure III and Xi and X ₂ may independent from each other be O, S, CH ₂ and NH. Generic group definition: Throughout the description and claims generic groups have been used, for example alkyl, alkoxy, aryl. Unless otherwise specified the following are preferred groups that may be applied to generic groups found within compounds disclosed herein: alkyl: linear and branched Cl-C8-alkyl, long-chain alkyl: linear and branched C5-C20 alkyl alkenyl: C2-C6-alkenyl, cycloalkyl: C3-C8-cyeloalkyl, alkoxy: Cl-C6-alkoxy, long-chain alkoxy: linear and branched C5-C20 alkoxy alkylene: selected from the group consisting of:

methylene; l,l-ethylene; 1, 2-ethylene; 1,1 -prop ylidene; 1, 2-propylene; 1,3- propylene; 2,2- propylidene; butan-2-ol-l,4-diyl; propan-2-ol-l,3-diyl; 1, 4-butylene; cyclohexane- 1, l-diyl; cyclohexan-l,2-diyl; cyclohexan-l,3- diyl; cyclohexan-l,4-diyl; cyclopentane- 1, l-diyl;

cyclopentan-l,2-diyl; and cyclopentan-l,3-diyl, aryl: selected from homoaromatic compounds having a molecular weight under 300, arylene: selected from the group consisting of: l,2-phenylene; 1,3- phenylene; l,4-phenylene;

1.2-naphtalenylene; l,3-naphtalenylene; 1,4- naphtalenylene; 2,3-naphtalenylene; 1 -hydroxy-

2.3 -phenylene; 1 -hydroxy-2,4- phenylene; 1 -hydroxy-2,5- phenylene; and 1 -hydroxy-2, 6- phenylene, heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; l,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridindiyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically preferred are: pyridin-2, 3-diyl; pyridin-2,4-diyl; pyridin-2,5-diyl; pyridin-2,6- diyl; pyridin-3,4- diyl; pyridin-3,5-diyl; quinolin-2, 3-diyl; quinolin-2,4-diyl; quinolin-2, 8- diyl; isoquinolin-l, 3-diyl; isoquinolin-l,4-diyl; pyrazol-l, 3-diyl; pyrazol-3,5- diyl; triazole-

3.5-diyl; triazole- 1, 3-diyl; pyrazin-2, 5-diyl; and imidazole-2, 4-diyl, a -C1-C6- heterocycloalkyl, wherein the heterocycloalkyl of the -Cl -C6-heterocyeloalkyl is, selected from the group consisting of: piperidinyl; piperidine; 1, 4-piperazine, tetrahydro thiophene; tetrahydrofuran; l,4,7-triazacyclononane; 1,4,8,11- tetraazacyclotetradecane; 1,4,7,10, 13- pentaazacyclopentadecane; l,4-diaza- 7-thia-cyclononane; 1,4- diaza-7-oxa-cyclononane; 1,4,7, lO-tetraazacyclododecane; l,4-dioxane; 1,4, 7-trithia-cyclononane; pyrrolidine; and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-l,2- ylene; piperidin-

2.6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylene; 1,4- piperazin-2,5-ylene; l,4-piperazin-2,6-ylene; l,4-piperazin- l,2-ylene; l,4-piperazin-l,3- ylene; l,4-piperazin-l,4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydro furan-2,5-ylene; tetrahydrofuran- 3,4-ylene;

tetrahydrofuran-2,3-ylene; pyrrolidin-2,5-ylene; pyrrolidin-3,4-ylene; pyrrolidin-2,3-ylene; pyrrolidin-l,2-ylene; pyrrolidin-l,3-ylene; pyrrolidin-2,2-ylidene; l,4,7-triazacyclonon-l,4- ylene; 1,4,7- triazacyclonon-2,3-ylene; l,4,7-triazacyclonon-2,9-ylene; l,4,7-triazacyclonon- 3,8-ylene; l,4,7-triazacyclonon-2,2- ylidene; l,4,8,l l-tetraazacyclotetradec-l,4-ylene;

1,4,8,11- tetraazacyclotetradec-l,8-ylene; 1,4,8, l l-tetraazacyclotetradec-2,3-ylene; 1,4,8,11- tetraazacyclotetradec-2,5-ylene; 1,4,8,11- tetraazacyclotetradec-l,2-ylene; 1,4,8,11- tetraazacyclotetradec-2,2-ylidene; 1 ,4,7,10-tetraazacyclododec- 1 ,4-ylene; 1 ,4,7,10- tetraazacyclododec-l,7-ylene; 1,4, 7,10-tetraazacyclododec- 1,2- ylene; 1,4,7,10- tetraazacyclododec-2,3- ylene; 1,4,7, l0-tetraazacyclododec-2,2-ylidene; 1,4,7,10,13 pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; 1,4,7,10, 13- pentaazacyclopentadec-2,3- ylene; l,4,7,l0,l3-pentaazacyclopentadec-l,2-ylene; 1,4,7,10, l3-pentaazacyclopentadec-2,2-ylidene; l,4-diaza-7-thia-cyclonon- l,4-ylene; l,4-diaza-7- thia-cyclonon-l,2-ylene; l,4-diaza-7thia-cyclonon- 2,3-ylene; l,4-diaza-7-thia-cyclonon-6,8- ylene; l,4-diaza-7-thia-cyclonon- 2,2-ylidene; l,4-diaza-7-oxacyclonon-l,4-ylene; l,4-diaza-

7-oxa-cyclonon- l,2-ylene; l,4diaza-7-oxa-cyclonon-2,3-ylene; l,4-diaza-7-oxa-cyclonon-6,

8-ylene; l,4-diaza-7-oxa-cyclonon-2,2-ylidene; l,4-dioxan-2,3-ylene; 1,4- dioxan-2,6-ylene;

1 ,4-dioxan-2,2-ylidene; tetrahydropyran-2,3-ylene; tetrahydropyran-2,6-ylene;

tetrahydropyran-2,5-ylene; tetrahydropyran-2,2- ylidene; l,4,7-trithia-cyclonon-2,3-ylene; l,4,7-trithia-cyclonon-2,9- ylene; and l,4,7-trithia-cyclonon-2,2-ylidene, heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; l,4-piperazinyl; tetrahydrothiophenyl;

tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8, 11 -tetraazacyclotetradecanyl; 1,4,7,10, 13- pentaazacyclopentadecanyl; l,4-diaza-7-thiacyclononanyl; l,4-diaza-7-oxa- cyclononanyl; 1,4,7, lO-tetraazacyclododecanyl; l,4-dioxanyl; 1,4,7- trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, amine: the group -N(R)2 wherein each R is independently selected from: hydrogen; C1-C6- alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl-C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, halogen: selected from the group consisting of: F; Cl; Br and I, halogenalkyl: selected from the group consisting of mono, di, tri-, poly and perhalogenated linear and branched Cl-C8-alkyl pseudohalogen: selected from the group consisting of -CN, -SCN, -OCN, N3, -CNO, -SeCN sulphonate: the group -S(0)20R, wherein R is selected from: hydrogen; Cl- C6-alkyl; phenyl; C 1 -C6-alkyl-C6H5 ; Li; Na; K; Cs; Mg; and Ca, sulphate: the group -0S(0)20R, wherein R is selected from: hydrogen; Cl- C6-alkyl; phenyl; C 1 -C6-alkyl-C6H5 ; Li; Na; K; Cs; Mg; and Ca, sulphone: the group -S(0)2R, wherein R is selected from: hydrogen; C1-C6- alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulphonamide) selected from the group: -NR'2, wherein each R’ is independently selected from: hydrogen; Cl-C6-alkyl; ClC6-alkyl-C6H5; and phenyl, wherein when both R' are Cl-C6-alkyl both R’ together may form an -NC3 to an -NCS heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, carboxylate derivative: the group -C(0)OR, wherein R is selected from: hydrogen; C1-C6- alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, carbonyl derivative: the group -C(0)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give amide) selected from the group: -NR'2, wherein each R’ is independently selected from: hydrogen; Cl- C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R’ are C1-C6- alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, phosphonate: the group -P(O) (OR) 2, wherein each R is independently selected from:

hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphate: the group -OP(0)(OR)2, wherein each R is independently selected from:

hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphine: the group -P(R)2, wherein each R is independently selected from: hydrogen; Cl- C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5, phosphine oxide: the group -P (O) R2, wherein R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5; and amine (to give phosphonamidate) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6- alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R' are Cl-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring. polyether: chosen from the group comprising-(0-CH ₂ -CH(R)) _n -OH and -(0-CH ₂ -CH(R)) _n -H whereby R is independently selected from: hydrogen, alkyl, aryl, halogen and n is from 1 to 250 silylalkyl: the group - S1R3, whereby each R is independently selected from: hydrogen; Cl- C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl-C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring Silylalkyloxy: the group - OS1R3, whereby each R is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are Cl-C6-alkyl both R together may form an - NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.

Unless otherwise specified the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein: alkyl: linear and branched Cl-C6-alkyl, more preferred methyl, ethyl, propyl, isopropyl, buyl, isobutyl long-chain alkyl: linear and branched C5-C10 alkyl, preferably linear C6-C8 alkyl alkenyl: C3-C6-alkenyl, cycloalkyl: C6-C8-cyeloalkyl, alkoxy: Cl-C4-alkoxy, long-chain alkoxy: linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy alkylene: selected from the group consisting of: methylene; 1, 2-ethylene; 1, 3-propylene; butan-2-ol-l,4-diyl; 1, 4-butylene; cyclohexane- 1, l-diyl; cyclohexan-l,2-diyl; cyclohexan-l,4- diyl; cyclopentane- 1, l-diyl; and cyclopentan-l,2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl, arylene: selected from the group consisting of: l,2-phenylene; 1,3- phenylene; l,4-phenylene;

1.2-naphtalenylene; l,4-naphtalenylene; 2,3- naphtalenylene and 1 -hydroxy-2, 6-phenylene, heteroaryl: selected from the group consisting of:

pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridin

2.3-diyl; pyridin-2,4-diyl; pyridin-2,6-diyl; pyridin-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4- diyl; isoquinolin-l,3-diyl; isoquinolin-l,4-diyl; pyrazol-3,5-diyl; and imidazole-2, 4-diyl, heterocycloalkyl: selected from the group consisting of:

pyrrolidinyl; morpholinyl; piperidinyl; piperidinyl; 1,4 piperazinyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8, 1 l-tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7, lO-tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of:

piperidin-2,6-ylene; piperidin-4,4-ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylene;

1.4-piperazin-2,6-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene;

tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; pyrrolidin-2,5-ylene; pyrrolidin-2,2- ylidene; l,4,7-triazacyclonon-l,4- ylene; l,4,7-triazacyclonon-2,3-ylene; 1,4,7- triazacyclonon-2,2-ylidene; 1,4,8,11- tetraazacyclotetradec-l,4-ylene; 1,4,8,11- tetraazacyclotetradec-l,8-ylene; 1,4,8, 1 l-tetraazacyclotetradec-2,3-ylene; 1,4,8, 11- tetraazacyclotetradec-2,2-ylidene; 1 ,4,7,10-tetraazacyclododec- 1 ,4-ylene; 1 ,4,7,10- tetraazacyclododec- 1 ,7-ylene; 1 ,4,7,10-tetraazacyclododec-2,3-ylene; 1 ,4,7 , 10- tetraazacyclododec-2,2-ylidene; 1,4,7,10,13- pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13- pentaazacyclopentadec-l,7-ylene; l,4-diaza-7-thia-cyclonon-l,4 ylene; l,4-diaza-7-thia- cyclonon-2,3-ylene; l,4-diaza-7-thia cyclonon-2,2-ylidene; l,4-diaza-7-oxa-cyclonon-l,4- ylene; 1,4 diaza-7-oxa-cyclonon-2,3-ylene;l,4-diaza-7-oxa-cyclonon-2,2- ylidene; 1,4- dioxan-2,6-ylene; l,4-dioxan-2,2-ylidene; tetrahydropyran-2,6-ylene; tetrahydropyran-2,5- ylene; and tetrahydropyran- 2,2-ylidene, a -Cl-C6-alkyl-heterocycloalky, wherein the heterocycloalkyl of the -Cl- C6-heterocyeloalkyl is selected from the group consisting of: piperidinyl; l,4-piperazinyl; tetrahydrofuranyl; 1,4,7- triazacyclononanyl; 1,4,8,11- tetraazacyclotetradecanyl; 1,4,7,10,13- pentaazacyclopentadecanyl; 1,4,7,10- tetraazacyclododecanyl; and pyrrolidinyl, wherein the heterocycloalkyl may be connected to the -C1-C6- alkyl via any atom in the ring of the selected heterocycloalkyl, amine: the group -N (R) 2, wherein each R is independently selected from: hydrogen; C1-C6- alkyl; and benzyl, halogen: selected from the group consisting of: F and Cl, sulphonate: the group -S(0)20R, wherein R is selected from: hydrogen; Cl- C6-alkyl; Na; K; Mg; and Ca, sulphate: the group -0S(0)20R, wherein R is selected from: hydrogen; Cl- C6-alkyl; Na; K; Mg; and Ca, sulphone: the group -S(0)2R, wherein R is selected from: hydrogen; C1-C6- alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, carboxylate derivative: the group -C(0)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; Cl-C6-alkyl; and benzyl, carbonyl derivative: the group: -C(0)R, wherein R is selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, phosphonate: the group -P(O) (OR)2, wherein each R is independently selected from:

hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphate: the group -OP(O) (OR)2, wherein each R is independently selected from:

hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphine: the group -P(R)2, wherein each R is independently selected from: hydrogen; Cl- C6-alkyl; and benzyl, phosphine oxide: the group -P(0)R2, wherein R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl. polyether: chosen from the group comprising-(0-CH ₂ -CH(R)) _n -OH and -(0-CH ₂ -CH(R)) _n -H whereby R is independently selected from: hydrogen, methyl, halogen and n is from 5 to 50, preferably 10 to 25.

M, Mn (n being an integer): Metals (either charged or uncharged), whereby two Metals Mn and Mm are independently selected from each other unless otherwise indicated.

According to a preferred embodiment the Ni(I)-compound may be monomeric, whereby the term“monomeric” is to be understood that the compound comprises only one nickel atom.

However, according to an alternative and also preferred embodiment the Ni(I)-compound may be dimeric, whereby the term“dimeric” is to be understood that the compound comprises two nickel atoms. If the Ni(I)-compound is dimeric then it is especially preferred that the Ni(I)-compound comprises a compound where there is a bond between the two nickel atoms. Especially preferred are compounds of the following structure:

With R ¹ and R ² being independent from each other electron donating ligands, especially phosphines and/or carbenes, most preferred carbenes and R ³ and R ⁴ independently from each other halogen, with chlorine being preferred, or pseudohalogen.

Especially preferred are compounds in which R ¹ and R ² as well as R ³ and R ⁴ are identical. Amongst these compounds, compounds are preferred where R ¹ and R ² is carbene and R ³ and R ⁴ is halogen. Many of these compounds can be formed in situ from suitable Ni(II) and Ni(0)precursors.

The inventive method can be carried out with or without a solvent. A solvent can be omitted when both the reactant and the product(s) are liquid with suitable viscosity.

If a solvent is used then non- or only weakly polar and non-protic solvents are preferred, especially chlorobenzene.

The content of the Ni(I)-compound (in mol% based on the alkene to be isomerized prior to the reaction) is preferably > 0.1 % to < 10%. A lower concentration of the Ni(I)-compound will prolong the reaction time, however the reaction will still occur. Preferred concentration which have been shown to be advantageous for most reactions are > 1 % to < 8%, preferred > 2 % to < 5%. The reaction time depends on the concentration of the Ni(I)-compound, however, reaction times between > 2 h to < 48 h are preferred.

The reaction can be carried out at ambient temperature, however also lower and higher temperatures are feasible. Preferred reaction temperatures are > 0 °C to < 40 °C, with > 20 °C to < 30 °C being preferred.

According to a preferred embodiment of the present invention, additionally to the Ni(I)- compound a Lewis-acid is present during the reaction. This has been shown for some applications to further increase the reaction speed and/or selectivity.

If a Lewis-acid is used then the preferred content (in mol% based on the alkene to be isomerized) is > 5% to < 20%, preferably > 10% to < 15%. Preferred Lewis acids include Ti(OiPr) ₄ , AlCb, CeCb, InCb, SbCb, BF ₃ .OEt ₂ , BCb, Sc(OTf) ₃ , Sn(O ^l Bu) ₄ and ZnCh, with Ti(OiPr) ₄ being especially preferred.

The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

Additional details, characteristics and advantages of the object of the invention are disclosed in the sub-claims and the following description of the respective examples -which in an exemplary fashion— show preferred embodiments according to the invention. Such embodiments do not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed. Synthesis of rNi(u-CP(IPr)l _{2 (} 1)

(1.97 equiv.)

Inside an Argon-filled glovebox, Ni(dme)Cl ₂ (280 mg, 1.27 mmol, 1.0 equiv.), Ni(cod) ₂ (350 mg, 1.27 mmol, 1.0 equiv.) and IPr (990 mg, 2.50 mmol, 1.97 equiv.) were suspended in toluene (20 mL). The resulting mixture was stirred at ambient temperature inside the glovebox for 18 h. The obtained mixture was filtered through a small pad of Celite in a fritted funnel and the filtrate concentrated to 8 mL under reduced pressure. Pentane (32 mL) was added to and the mixture was cooled at -25 °C overnight. The formed crystals were collected by filtration and washed with cold pentane (3 x 2 mL) to afford Ni(I) dimer 1 as greenish yellow crystals in 53% yield (660 mg, 0.68 mmol). General method for isomerization of alkenes:

terminal olefin (E)-olefin Inside an Argon-filled glovebox, [Ni(q-CI)(IPr)] ₂ (1, 5 mol%) was weighed into a vial and a solution of the alkene to be isomerized (1.0 equiv.) in CI-C6H5 (0.4M) was added. The reaction vial was sealed with a screw cap and reaction mixture was stirred at ambient temperature inside the glovebox for 3 h (unless otherwise specified). The obtained solution was directly loaded onto a silica column for purification (using pentane/ether as eluent) to afford the reaction product. Examples:

Using the above general method, the following alkenes were prepared from the corresponding terminal alkenes: Reaction product Yield E/Z-Ratio Remark

The following dialkenes were synthesized using the above general method as follows:

The appendix c) in the second reaction indicates that 10% Ni(I)-compound 1 was used.

Using the above general method, the following trisubstituted alkenes were prepared.

Reactant Reaction product Yield Remark . y For compound with remarks“calculated” the yield was calculated using l,3,5-tri-tert.butyl benzene as internal standard.

Additionally, the synthesis of the following alkenes from the terminal alkenes involving a longer“chain-walk” was conducted, giving the following results:

Reaction product Yield E/Z-Ratio

99% (cal.)

87%(cal.) 99: 1

88%(cal.) 98:2

85%(cal.) 98:2

99%(cal.) 98%(cal.) ² >99: 1 .

Entries markes with“ ² ” : The yield was calculated using l,3-benzodioxole as internal standard.

It can be seen that for longer carbon chains the yields are lower (though in most applications nearly quantitative conversion occurs), however the E/Z ratio is still >99:1.

The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated.

As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.