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US 6,191,284 B1Granted
Ligands and complexes for enantioselective hydrogenation
AssigneeDegussa-Huels Aktiengesellschaft
InventorsPaul Knochel, Tanja Ireland, Gabriele Grossheimann, Karlheinz Drauz, Ingo Klement
Life of this patent
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Abstract
A ferroceneylphosphine ligand and complexes prepared therefrom for homogeneous catalytic enantioselective hydrogenation, the ligand having the formula (I): Another aspect of the invention is directed to a ferroceneylphosphine ligand of formula (II),
Claims14
An enantiomer-enriched ligand of formula (I) and salts thereof:
- wherein R1 and R2, independent of one another, are R8, NR6R7, SR6, (C1-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxylalkyl, (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)-heteroalkyl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl;
- or R1 and R2 are bonded via a (C3-C7) carbocycle, which can be substituted one or more times by linear or branched (C1-C,)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or can contain heteroatoms like N, O, P, S in the ring;
- R3 and R4, independent of one another, are H, (C1-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxylalkyl, (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)-heteroalkyl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl;
- or R3 and R4 are bonded via a (C3-C5) bridge, optionally containing at least one double bond and/or optionally substituted by at least once by linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or optionally contains at least one heteroatom selected from the group consisting of N, O, P and S in the ring;
- R5 is (C1-C18)-alkyl, (C6-C18)-aryl, (C3-C18)-heteroaryl, (C1-C8)-alkyl-(C6-C18)-aryl, (C1-C8)-alkyl-(C3-C19)-heteroalkyl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl, where the residues R5 on the same phosphorus atom and/or the two phosphorus atoms can be different;
- R6 and R7, independent of one another, are H, (C1-C18)-alkyl, (C1-C8)-alkoxy, (C2-C8)-alkoxylalkyl, (C1-C8)-acyl, (C6-C18)-aryl, (C7-C19)-aralkyl, (C3-C18)-heteroaryl, (C4-C19)-heteroaralkyl, (C1-C8)-alkyl-(C6-C18)-alkyl, (C1-C8)-alkyl-(C3-C19)-heteroalkyl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl (C3-C8)-cycloalkyl, (C3-C8)-cycloalkyl-(C1-C8)-alkyl;
- or R6 and R7 are bonded via a (C3-C7) carbocycle, which optionally is substituted at least once by linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or the carbocycle optionally containing at least one heteroatom selected from the group consisting of N, O, P and S in the ring;
- R8 is H or a radical B-X-Z, wherein B is a radical selected from the group consisting of CR92, NR9, O, S or SiR92, X is a spacer selected from the group consisting of 1,4′-biphenyl, 1- or 2-ethylene, 1- or 3-propylene and PEG-(2-10) and Z is a radical bonded to a polymer via a functional group selected from the group consisting of O—, NH—, COO—, CONH, ethenyl, NHCONH—, OCONH— and NHCOO—;
- or the residues R8 of the two cyclopentadienyl rings are bonded to each other via an α,ω-(C2-C4)-alkylene bridge;
- and
- R9 is H or (C1-C18)-alkyl.
8 more elements
An enantiomer enriched complex of formula (II) and salts thereof:
- R1 and R2, independent of one another, are R8, NR6R7, SR6, (C1-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxylalkyl, (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)-heteroalkyl, (C3-C8)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl and (C3-C8)-cycloalkyl-(C1-C8)-alkyl;
- or R1 and R2 are bonded via a (C3-C7) carbocycle, which is optionally substituted at least once by linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or optionally contains at least one heteroatom selected from the group consisting of N, O, P and S in the ring;
- R3 and R4, independent of one another, are H, (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)-heteroalkyl, (C3-C18)-cycloalkyl, (C1-C8)-alkyl-(C3-C8)-cycloalkyl and (C3-C,)-cycloalkyl-(C1-C8) alkyl;
- or R3 and R4 are bonded via a (C3-C5)-bridge, which optionally contains at least one double bond and/or optionally is substituted at least once by linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or optionally contains at least one heteroatom selected from the group consisting of N, O, P and S in the ring;
- R5 is (C1-C18)-alkyl, (C6-C18)-aryl, (C3-C18)-heteroaryl, (C1-C8)-alkyl-(C6-C18)-aryl;
- (C1-C8)-alkyl-(C3-C19) heteroalkyl, (C3-C8) cycloalkyl or (C1-C8)-alkyl-(C3-C8)-cycloalkyl, where the radicals R5 on the same phosphorus atom and/or the two phosphorus atoms optionally are different;
- R6 and R7, independent of one another, are H, (C1-C18)-alkyl, (C1-C18)-alkoxy, (C2-C18)-alkoxylalkyl, (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)-heteroalkyl, (C3-C8)-cycloalkyl, (C1-C,)-alkyl-(C3-C8)-cycloalkyl or (C3-C8)-cycloalkyl-(C1-C8)-alkyl;
- or R6 and R7 are bonded via a (C3-C7)-carbocyclc, which optionally is substituted at least once by linear or branched (C1-C8)-alkyl, (C1-C8)-acyl, (C1-C8)-alkoxy, (C2-C8)-alkoxyalkyl and/or optionally contains at least one heteroatom selected from the group consisting of N, O, P and S in the ring;
- R8 is H or a radical B-X-Z, where B is a radical selected from the group consisting of CR92, NR9, O, S and SiR92, X is a spacer selected from the group consisting of 1,4′-biphenyl, 1- or 2-ethylene, 1- or 3-propylene and PEG-(2-10) and Z is a radical bonded to a polymer via a functional group selected from the group consisting of —O—, —NH—, —COO—, —CONH, -ethenyl, —NHCONH—, —OCONH— or —NHCOO—;
- or the radicals R8 of the two cyclopentadienyl rings are bonded to each other via an α,ω-(C2-C4)-alkylene bridge,
- R9 is H or (C1-C18) alkyl,
- and M is a metal atom or ion selected from the group consisting of Co, Ni, Rh, Ru, Ir, Pd, Re and Pt.
9 more elements
Dependencies are inferred from the claim text.