Patent ID: 6348620
Filing Date: 2002-02-19
Classification: C07B,C07C,Y02P

Abstract:
A method for the homogeneous, catalytic, enantioselective hydrogenation of a compound of formula (I) or R and Râ€² or Râ€² and Râ€³ or Râ€³ and R are connected to one another via a (C1-C4) bridge which can be singly or multiply substituted with linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl groups and/or can contain heteroatoms selected from the group consisting of N, O, P, and S in the ring,said method comprising contacting said compound with a catalyst of formula (II) in whichR1, R2 signify, independently of one another, H, NR6R7, SR6, (C1-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxyalkyl, (C1-C18)-acyloxy, (C6-C18)-aryl, (C7-C19)-aralkyl, (C3-C18)-heteroaryl, (C4-C19)-heteroaralkyl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroaryl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl, in whichn is a whole number from 0 to 3, R&boxH;H, (C1-C18)-alkyl, (C6-C18)-aryl, (C7-C19)-aralkyl, (C3-C18)-heteroaryl, (C4-C19)-heteroaralkyl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroaryl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl, or signifies a carboxy protective group, Râ€²&boxH;H, (C1-C18)-alkyl, (C6-C18)-aryl, (C7-C19)-aralkyl, (C3-C18)-heteroaryl, (C4-C19)-heteroaralkyl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroaryl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl, which groups just cited can be substituted with (C1-C8)-acyl or (C1-C8)-alkyloxycarbonyl, X&boxH;O, CHRâ€³, NRâ€³, NNHRâ€³, Râ€³ can be &boxH;H, OH, Râ€², (C1-C18)-alkoxy, (C2-C18)-alkoxyalkyl, (C1-C18)-acyl, (C1-C18)-acyloxy and Râ€³ can assume different shapes for different positions in the molecule, or R1 and R2 are connected via a (C3-C7)-carbocycle which can be singly or multiply substituted with linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or can contain heteroatoms selected from the group consisting of N, O, P, and S in the ring, R3 signifies (C2-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxyalkyl, (C1-C18)-acyloxy, (C6-C18)-aryl, (C7-C19)-aralkyl, (C3-C18)-heteroaryl, (C4-C19)-heteroaralkyl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroaryl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl, R4 signifies (C1-C18)-alkyl, (C6-C18)-aryl, (C3-C18)-heteroaryl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroaryl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, R5 signifies H or a group B-X-Z in which B is a residue selected from the group consisting of CR82, NR8, O, S, and SiR82, X is a spacer selected from the group consisting of 1,4â€²-biphenyl, 1-, 2-ethylene, 1-, 3-propylene, and PEG-(2-10), and Z signifies a group bound to a polymer via a functional group selected from Oâ€”, NHâ€”, COOâ€”, CONHâ€”, ethenylâ€”, NHCONHâ€”, OCONHâ€” or NHCOOâ€”, or the groups R5 of the two cyclopentadienyl rings are connected to each other via an &agr;, &ohgr;-(C2-C4)-alkylene bridge, R6, R7 signify, independently of one another, H, (C1-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxyalkyl, (C1-C18)-acyl, (C6-C18)-aryl, (C7-C19)-aralkyl, (C3-C18)-heteroaryl, (C4-C19)-heteroaralkyl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroaryl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl, or R6 and R7 are connected via a (C3-C7)-carbocycle which may be substituted singly or multiply with linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and or can contain heteroatoms selected from the group consisting of N, O, P, and S in the ring, R8 signifies H, (C1-C18)-alkyl and M is a metal atom or metal ion of subgroup 7 or 8.