Use of ferrocenyl ligands for catalytic, enantioselective...

Details Use of ferrocenyl ligands for catalytic, enantioselective... Use of ferrocenyl ligands for catalytic, enantioselective...

1999-06-18

2001-09-04

Yildirim, Bekir L. (Department: 1764)

Organic compounds -- part of the class 532-570 series

Organic compounds

Amino nitrogen containing

C554S143000, C554S145000, C556S018000, C585S260000

Reexamination Certificate

active

06284925

ABSTRACT:

CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from German Applications No. 198 27 311.8, filed on Jun. 19, 1998 and 199 21 924.9 filed on May 12, 1999, the subject matter of each of which is hereby incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the use of enantiomer-enriched ligands of the general formula I and their salts
in which
R
1
, R
2
, R
3
signify, independently of each other, H, NR
6
R
7
, SR
6
, (C
1
-C
8
)-alkyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, (C
1
-C
8
)acyloxy, which can be optionally present as linear or branched and can be substituted singly or multiply with halogens, with groups containing N, O, P, S atoms,
(C
3
-C
7
)-cycloalkyl, which can be substituted singly or multiply with linear or branched (C
1
-C
8
)-alkyl, 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 such as 1-, 2-, 3-, 4-piperidyl, such as 1-, 2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl,
(C
6
-C
18
)-aryl, such as phenyl, 1-, 2-naphthyl or anthryl, (C
6
-C
18
)-aralkyl, such as benzyl or 1,1-, 1,2-phenethyl, (C
5
-C
18
)-heteroaryl, such as 2-, 3-furyl, 2-, 3-pyrrolyl, 2-, 3-, 4-pyridyl,
(C
6
-C
18
)-heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, 1-, 2-furylethyl, 1-, 2-pyrrolylethyl, 1-, 2-pyridylethyl, which aryl, aralkyl, heteroaryl or heteroaralkyl groups can optionally be substituted singly or multiply with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-acyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, which can 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
1
and R
2
are joined in a (C
3
-C
7
)-carbocycle which can be substituted singly or multiply with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-acyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, which can 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
4
signifies (C
1
-C
8
)-alkyl, (C
6
-C
18
)-aryl, such as phenyl, 1-, 2-naphthyl, 2,2′-biphenyl or anthryl,1-pyrrolyl, and the just-cited groups can be optionally substituted with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, which can 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
3
-C
7
)-cycloalkyl, which can be singly or multiply substituted with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-alkoxy, (C
2
-C
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
5
signifies H or a group B—X—Z in which B is a group selected from CR
8
2
, NR
8
, O, S, and SiR
8
2
, X is a spacer such as, e.g., 1,4′-biphenyl, 1-, 2-ethylene, 1-, 3-propylene, PEG-(2-10) and Z is a group bound to a polymer via a functional group such as, e.g., the O—, NH—, COO—, CONH—, ethenyl—, NHCONH—, OCONH— or NHCOO— function, or the groups R
5
of the two cyclopentadienyl rings are connected to each other via an &agr;, &ohgr;-(C
2
-C
4
)-alkylene bridge,
R
6
, R
7
signify, independently of one another, H, (C
1
-C
8
)-alkyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, (C
1
-C
8
)-acyl, which are optionally linear or branched and can be singly or multiply substituted with halogens, with groups containing N, O, P, S atoms,
(C
3
-C
7
)-cycloalkyl, which can be substituted singly or multiply with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-acyl, (C
1
-C
8
)-alkoxy, (C
2
-C
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 such as 1-, 2-, 3-, 4-piperidyl, such as 1,2-, 3-pyrrolidinyl, 2-, 3-tetrahydrofuryl, 2-, 3-, 4-morpholinyl, (C
6
-C
18
)-aryl, such as phenyl, 1-, 2-naphthyl or anthryl, (C
6
-C
18
)-aralkyl, such as benzyl or 1,1-, 1,2-phenethyl, (C
5
-C
18
)-heteroaryl, such as 2-, 3-furyl, 2-, 3-pyrrolyl, 2-, 3-, 4-pyridyl, (C
6
-C
18
)-heteroaralkyl, such as furfuryl, pyrrolylmethyl, pyridylmethyl, 1-, 2-furylethyl, 1-, 2-pyrrolylethyl, 1-, 2-pyridylethyl,
which aryl, aralkyl, heteroaryl or heteroaralkyl groups can optionally be substituted singly or multiply with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-acyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, which can 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
6
and R
7
are joined in a (C
3
-C
7
) carbocycle, which can be substituted singly or multiply with linear or branched (C
1
-C
8
)-alkyl, (C
1
-C
8
)-acyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, which can 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, and
R
8
signifies H, (C
1
-C
8
)-alkyl for homogeneous, catalytic, enantioselective hydrogenation.
Moreover, the invention concerns the use of enantiomer-enriched complexes of the general formula II and their salts
in which
R
1
to R
8
have the meanings indicated above and M is a metal atom or metal ion of the subgroup [B group] 8, e.g., Ni, Co, Rh, Ru, Ir, Pd, Re or Pt for enantioselective, homogeneous, catalytic hydrogenation.
2. Background Information
The homogeneous, catalytic, enantioselective hydrogenation of imines and enamines is of great interest for the production of, e.g., amino acids enriched with enantiomers since the latter are required for their part as chiral educts in the organic synthesis, e.g., of bioactive active substances.
The use of bisphosphine catalysts for the enantioselective, homogeneous, catalytic hydrogenation for the purpose just cited is well known (Burk et al., Tetrahedron 1994, 4399).
Hayashi et al. (J. Chem. Soc., Chem Commun. 1989, 495-496), Knochel et al. (Chem. Eur. J. 1998, 4, 950-968) and Ikeda et al. (Tetrahedron Lett. 1996, 4545-4548) describe Pd complexes with C
2
-symmetric ferrocenyl-(bis-tertiary phosphine) ligands. However, these complexes were used solely in asymmetric allylations and cross couplings. The use of ligands in enantioselective hydrogenation was not known up to the present.
Yamamoto at al. (Bull. Chem. Soc. Jpn. 1980, 53, 1132-1137) reported about the use of non C
2
-symmetric ferrocenyl-(bis-tertiary phosphine) ligands in enantioselective, homogeneous, catalytic hydrogenation. However, good excesses of enantiomers are obtained only very sporadically with these ligands.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method using C
2
-symmetric, enantiomer-enriched bisphosphine ligand systems and -catalysts for the homogeneous, enantioselective, catalytic hydrogenation of multiple bonds.
The term “multiple bonds” denotes in the framework of the invention double bonds between a carbon atom and another carbon atom or nitrogen atom.
As a result of the fact that the enantiomer-enriched ligands of the general formula I and their salts are used for the homogeneous, catalytic, enantioselective hydrogenation of multiple bonds,
in which
R
1
, R
2
, R
3
signify, independently of each other, H, NR
6
R
7
, SR
6
, halogen, (C
1
-C
8
)-alkyl, (C
1
-C
8
)-alkoxy, (C
2
-C
8
)-alkoxyalkyl, (C
1
-C
8
)-acyloxy, which can be optionally present as linear or branched as well as can be substituted singly or multiply with halogens, with groups containing N, O, P, S atoms,
(C

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