Patent ID: 6284925
Filing Date: 2001-09-04
Classification: C07B,C07C

Abstract:
A method for the homogeneous, catalytic, enantioselective hydrogenation of C.dbd.C and C.dbd.N double bonds comprising using an enantiomer-enriched ligand of general formula I, or salt thereof ##STR14##in whichR.sup.1, R.sup.2, R.sup.3 signify, independently of each other, H, NR.sup.6 R.sup.7, SR.sup.6, (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, (C.sub.1 -C.sub.8)acyloxy, which are linear or branched and may be substituted singly or multiply with halogens, with groups containing N, O, P, S atoms,(C.sub.3 -C.sub.7)-cycloalkyl, which may be substituted singly or multiply with linear or branched (C.sub.1 -C.sub.8)-alkyl, which may be optionally substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms and/or may contain heteroatoms such as N, O, P, S in the ring such as 1-, 2-, 3-, 4-piperidyl, such as 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl,(C.sub.6 -C.sub.18)-aryl, such as phenyl, 1-, 2-naphthyl or anthryl, (C.sub.6 -C.sub.18)-aralkyl, such as benzyl or 1,1-, 1,2-phenethyl, (C.sub.5 -C.sub.18)-heteroaryl, such as 2-, 3-furyl, 2-, 3-pyrrolyl, 2-, 3-, 4-pyridyl,(C.sub.6 -C.sub.18)-heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, 1-, 2-furylethyl, 1-, 2-pyrrolylethyl, 1-, 2-pyridylethyl, which aryl, aralkyl, heteroaryl or heteroaralkyl groups may optionally be substituted singly or multiply with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-acyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which may be substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms,or R.sup.1 and R.sup.2 are joined in a (C.sub.3 -C.sub.7)-carbocycle which can be substituted singly or multiply with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-acyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which may optionally be substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms and/or can contain heteroatoms such as N, O, P, S in the ring,R.sup.4 signifies (C.sub.1 -C.sub.8)-alkyl, (C.sub.6 -C.sub.18)-aryl, such as phenyl, 1-, 2-naphthyl, 2,2'-biphenyl or anthryl,1-pyrrolyl, and the just-cited groups may be optionally substituted with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which may be substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms,(C.sub.3 -C.sub.7)-cycloalkyl, which may be singly or multiply substituted with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which can be optionally substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms and/or can contain heteroatoms such as N, O, P, S in the ring,R.sup.5 signifies H or a group B--X--Z in which B is a residue selected from the group consisting of CR.sup.8.sub.2, NR.sup.8, O, S, and SiR.sup.8.sub.2, X is a spacer selected from the group consisting of 1,4'-biphenyl, 1-, 2-ethylene, 1-, 3-propylene, and PEG-(2-10) and Z is a group bound to a polymer via a functional group selected from O--, NH--, COO--, CONH--, ethenyl-, NHCONH--, OCONH-- and NHCOO--,or the groups R.sup.5 of the two cyclopentadienyl rings are connected to each other via an .alpha., .omega.-(C.sub.2 -C.sub.4)-alkylene bridge,R.sup.6, R.sup.7 signify, independently of one another, H, (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, (C.sub.1 -C.sub.8)-acyl, which are linear or branched and may be singly or multiply substituted with halogens, with groups containing N, O, P, S atoms,(C.sub.3 -C.sub.7)-cycloalkyl, which may be substituted singly or multiply with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-acyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which may optionally be substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms and/or may contain heteroatoms such as N, O, P, S in the ring such as 1-, 2-, 3-, 4-piperidyl, such as 1,2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl, (C.sub.6 -C.sub.18)-aryl, such as phenyl, 1-, 2-naphthyl or anthryl, (C.sub.6 -C.sub.18)-aralkyl, such as benzyl or 1,1-, 1,2-phenethyl, (C.sub.5 -C.sub.18)-heteroaryl, such as 2-, 3-furyl, 2-, 3-pyrrolyl, 2-, 3-, 4-pyridyl, (C.sub.6 -C.sub.18)-heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, 1-, 2-furylethyl, 1-, 2-pyrrolylethyl, 1-, 2-pyridylethyl, which aryl, aralkyl, heteroaryl or heteroaralkyl groups may optionally be substituted singly or multiply with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-acyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which may be substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms,or R.sup.6 and R.sup.7 are joined in a (C.sub.3 -C.sub.7) carbocycle, which may be substituted singly or multiply with linear or branched (C.sub.1 -C.sub.8)-alkyl, (C.sub.1 -C.sub.8)-acyl, (C.sub.1 -C.sub.8)-alkoxy, (C.sub.2 -C.sub.8)-alkoxyalkyl, which may optionally be substituted singly or multiply with halogens, groups containing N, O, P, S atoms, with halogens, with groups containing N, O, P, S atoms, and/or can contain heteroatoms such as N, O, P, S in the ring, andR.sup.8 signifies H, (C.sub.1 -C.sub.8)-alkyl.