Process for the ruthenium catalyzed

1. A process for highly stereoselective trans-hydrostannation of alkynes comprising the steps of reacting an alkyne of the formula (I)

with a tin hydride of the formula X 1 X 2 X 3 SnH in the presence of a ruthenium catalyst to yield an alkene of the formula (II):

Wherein:

R 1 and R 2 are the same or different and are each selected from:

I. straight chain or branched chain aliphatic hydrocarbons, or cyclic aliphatic hydrocarbons, said aliphatic hydrocarbons optionally having heteroatoms and/or aromatic hydrocarbons and/or heteroaromatic hydrocarbons in the chain and/or having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, or heteroatoms, or

II. aromatic hydrocarbons having 5 to 20 carbon atoms or heteroaromatic hydrocarbons having 1 to 20 carbon atoms, said aromatic or heteroaromatic hydrocarbons each optionally having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, heteroatoms, or

one of R 1 and R 2 is selected from hydrogen, halogen, or —SiR*R**R***, wherein R*, R**, R*** can be the same or different and shave the meaning as given under I. and II., and the other of R 1 and R 2 has the meaning as given under I, and II, or

R 1 and R 2 together form an aliphatic hydrocarbon chain having 6 to 30 carbon atoms, optionally having heteroatoms and/or aromatic hydrocarbons in the chain and/or optionally having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, said aliphatic hydrocarbon chain optionally being substituted by one or more substituents selected from heterosubstituents, straight chain, branched chain, cyclic aliphatic C 1 to C 20 hydrocarbons, C 6 to C 20 aromatic hydrocarbon, C 5 to heteroaromatic hydrocarbon, aryl-(C 1 -C 6 )-alkyl, or heteroaryl-(C 1 -C 6 )-alkyl or heteroatoms;

wherein the substituents X 1 , X 2 and X 3 in the formula X 1 X 2 X 3 SnH are the same or different and are each selected from hydrogen, straight chain, branched chain or cyclic aliphatic hydrocarbons, aromatic hydrocarbons, or two of X 1 X 2 and X 3 together form an aliphatic hydrocarbon chain having 2 to 20 carbon atoms, said hydrocarbon group optionally having heteroatoms in the chain and/or optionally having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 1 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, having identical or different alkyl groups with 2 to 12 carbon atoms, halogen or heteroatoms wherein at least two of X 1 , X 2 and X 3 are not hydrogen; and

wherein the catalyst is a cyclopentadienyl-coordinated ruthenium complex containing the following substructure:

wherein R cp1 to R cp5 are the same or different and are each selected from hydrogen or from straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having heteroatoms and/or aromatic hydrocarbons in the chain and/or optionally having one or more substituents selected from C 1 -C 20 -alkyl, heterocycloalkyl, C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl or heteroatoms and wherein further ligands are coordinated to the central atom Ruthenium.

2. Process for highly stereoselective trans-hydrostannation of alkynes according to claim 1 wherein R 1 and R 2 are the same or different and are each selected from straight chain or branched chain aliphatic hydrocarbons having 1 to 20 carbon atoms optionally having heteroatoms and/or aromatic hydrocarbons in the chain or aromatic hydrocarbons having 5 to 20 carbon atoms, optionally having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, or heteroatoms, or

R 1 and R 2 together form an aliphatic hydrocarbon chain structure having 8 to 20 carbon atoms, optionally having heteroatoms and/or aromatic hydrocarbons in the chain and/or optionally having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, said chain structure optionally being substituted by one or more substituents selected from heterosubstituents, straight chain, branched chain, cyclic aliphatic C 1 to C 20 hydrocarbons, C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon, aryl-(C 1 -C 6 )-alkyl, or heteroaryl-(C 1 -C 6 )-alkyl, or

one of R 1 and R 2 is selected from hydrogen, halogen, —SiR*R**R***, wherein R*, R**, R*** are the same or different and are each selected from straight chain or branched chain aliphatic hydrocarbons having 1 to 20 carbon atoms optionally having heteroatoms and/or aromatic hydrocarbons in the chain or aromatic hydrocarbons having 5 to 20 carbon atoms, optionally having one or more substituents selected from C 1 -C 20 -alkyl, C 5 -C 8 -heterocycloalkyl or C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl, or heteroatoms.

3. Process for highly stereoselective trans-hydrostannation of alkynes according to claim 1 wherein the substituents X 1 , X 2 and X 3 in the formula X 1 X 2 X 3 SnH are the same or different and are each selected from straight chain, branched chain or cyclic C 1 to C 10 aliphatic hydrocarbons each optionally being substituted by methyl, ethyl, propyl, butyl or isomers thereof, or one or more fluorine atoms.

4. Process for highly stereoselective trans-hydrostannation of alkynes according to claim 1 wherein the catalyst used in the inventive process is a cyclopentadienyl-coordinated ruthenium complex comprising the following substructure:

wherein R cp1 to R cp5 are the same or different and are each selected from hydrogen or from straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having heteroatoms and/or aromatic hydrocarbons in the chain and/or optionally having one or more substituents selected from C 1 -C 20 -alkyl, heterocycloalkyl, C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl or heteroatoms and wherein further ligands coordinated to the central atom ruthenium.

5. Process for highly stereoselective trans-hydrostannation of alkynes according claim 1 wherein the catalyst is [Cp*RuL 3 ]X wherein Cp*=η 5 -C 5 R 5cp with each R cp being H or CH 3 , and L being the same or different ligand/substituent and being selected from electron-donating ligands/substituents, or wherein the catalyst is a complex of the formula [Cp*RuY n ] wherein Cp*=η 5 -C 5 R 5cp with each R cp being H or CH 3 , and Y is an anionic ligand being selected from hydrogen, halogen and n=2, 3, or a dimer or oligomer of the formula [Cp*RuY 2 ] n wherein Cp*=η 5 -C 5 R 5 with R being H or CH 3 and Y is an anionic ligand and being selected from hydrogen, halogen and n≧2.

6. Process for highly stereoselective trans-hydroboration of internal alkynes according to claim 1 wherein the following complex is used as catalyst:

wherein the substituent R is selected from H or Me and X ⊖ is an anionic counter ion.

7. Process for highly stereoselective trans-hydrostannation of alkynes according to claim 5 wherein the anionic counterion is selected from PF 6 , SbF 6 − , BF 4 − , ClO 4 − , F 3 CCOO − , Tf 2 N − , (Tf=trifluoromethanesulfonyl), TfO − , tosyl, [B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ] − , B(C 6 F 5 ) 4 − or Al(OC(CF 3 ) 3 ) 4 − .

8. Process for highly stereoselective trans-hydrostannation of alkynes according to claim 1 wherein the catalyst is selected from the following complexes:

wherein the substituent X is selected from Cl, Br, I, and n is ≧2.

9. Process for highly stereoselective trans-hydrostannation of unsymmetrical alkynes according to claim 1 , in which the catalyst is selected depending on the alkyne in order to control the ratio of regioisomers formed.

10. A process comprising conducting a hydrostannation reaction in the presence of an organic tin compound and a catalyst, wherein the catalyst is a ruthenium catalyst comprising a cyclopentadienyl-coordinated ruthenium complex comprising the following substructure:

wherein R cp1 to R cp5 are the same or different and are each selected from hydrogen or from straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having heteroatoms and/or aromatic hydrocarbons in the chain and/or optionally having one or more substituents selected from C 1 -C 20 -alkyl, heterocycloalkyl, C 6 to C 20 aromatic hydrocarbon, C 5 to C 20 heteroaromatic hydrocarbon or aryl-(C 1 -C 6 )-alkyl, heteroaryl-(C 1 -C 6 )-alkyl or heteroatoms and wherein further ligands L are coordinated to the central atom ruthenium.