Process for hydrocyanation of terminal alkynes
AssigneeStudiengesellschaft Kohle mbH
InventorsTobias Ritter, Fei Ye
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Abstract
The present invention refers to a process for a Rh-catalyzed Anti-Markovnikov hydrocyanation of terminal alkynes which process discloses, for the first time, the highly stereo- and regio-selective hydrocyanation of terminal alkynes to furnish E-configured alkenyl nitriles and the catalyst used in the present process.
Claims7
A process for hydrocyanation of terminal alkynes comprising reacting a terminal alkyne (I) with at least one —CN source selected from the group consisting of HCN and cyanohydrine (II) in the presence of a Rh-complex to obtain an E-alkenyl nitrile (III):
- wherein R is i) a straight chain, branched chain or cyclic aliphatic C1 to C20 hydrocarbon, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aryl, (C1-C6)-alkyl-C6 to C20-aryl, (C1-C6)-alkyl-C5 to C20-heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aryl, (C1-C6)-alkyl-C6 to C20-aryl, (C1-C6)-alkyl-C5 to C20-heteroaryl or heterosubstituents;
- or ii) SiRIRIIRIII, wherein RI, RII, and RIII may be same or different and each stands for a straight chain, branched chain or cyclic aliphatic C1 to C20 hydrocarbon, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aryl, (C1-C6)-alkyl-C6 to C20-aryl, C5 to C20-heteroaryl, (C1-C6)-alkyl-C5 to C20-heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aryl, (C1-C6)-alkyl-C6 to C20-aryl, (C1-C6)-alkyl-C5 to C20-heteroaryl or heterosubstituents;
- wherein R1 and R2 may be same or different and each stands for a straight chain, branched chain or cyclic aliphatic C1 to C20 hydrocarbon, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aryl, (C1-C6)-alkyl-C6 to C20-aryl, (C1-C6)-alkyl-C5 to C20-heteroaryl, each hydrocarbon optionally being substituted by one or more groups selected from C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, C3-C8-heterocycloalkyl, C6 to C20 aryl, (C1-C6)-alkyl-C6 to C20-aryl, (C1-C6)-alkyl-C5 to C20-heteroaryl or heterosubstituents;
- wherein cat RhI stands for a Tp-Rhodium complex with a mono- or bidentate phosphine, and
- wherein solvent stands for an organic solvent.
Tp-Rhodium complex with a bidentate phosphine ligand whereby the residues of the Tp ((tris(1-pyrazolyl)borate anion) and/or the bidentate phosphine ligand are optionally substituted with electro-donating substituent(s).
Tp-Rhodium complex with a mono- or bidentate phosphine ligand whereby the mono- or bidentate phosphine ligand is selected from dppf (1,1′-bis(diphenylphosphino)ferrocene), dppm (1-bis(diphenylphosphino)methane), dppe (bis(diphenylphosphino)ethan), xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), PCy3 (tricyclohexylphosphine), PPh3 (triphenylphosphine), BINAP (2,2′ bis(diphenylphosphino)-1,1′-binaphthyl), and DPE-phos (bis[2-(diphenylphosphino) phenyl]ether.
Dependencies are inferred from the claim text.