Chiral ferrocenyls

Details Chiral ferrocenyls Chiral ferrocenyls

1999-03-08

2000-10-17

Nazario-Gonzalez, Porfirio

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

Organic compounds

Heavy metal containing

556 22, 556 28, 556145, 549313, 549325, 560 24, 560 41, C07F 1702, C07F 1900

Patent

active

061334642

DESCRIPTION:

BRIEF SUMMARY
The invention relates to chiral ferrocenes substituted in the 1- and 1'-positions by two different radicals and also substituted in the 2-position, according to the general formula (I), to processes for their preparation and to the use thereof as ligands in catalysis.
Metal complexes having chiral ferrocenyl ligands are known as catalysts for a number of reactions (e.g. enantioselective hydrogenation, hydrosilylation, formation of C--C bonds). The task of the chiral ligands is firstly so to adjust the electronic environment on the metal that a catalystic cycle becomes possible and secondly to transfer the chiral information to the substrate. Hitherto there has been no model that makes it possible to predict which chiral ligand will be best (especially in respect of enantioselectivity) for the catalytic reaction of a substrate. It is therefore advantageous if the electronic and steric properties of a ligand can be coordinated within a wide range both roughly and precisely.
Most of the diphosphine ligands described hitherto, however, contain two identical phosphines. That applies also to the chiral ferrocenyl ligands described by T. Hayashi et al. which have already been used successfully in a large number of catalytic reactions. Those ligands correspond, for example, to the following formula: ##STR2## and are described in T. Hayashi, Ferrocenes (Ed.: A. Togni and T. Hayashi), VCH Publishers New York (1995) 105-142.
Examples of chiral ferrocenyl ligands having at least one sulfur radical are: ##STR3## C. K. Lai, A. A. Naiini and C. H. Brubaker, Inorg. Chim. Acta, 164 (1989) 205-10. ##STR4## C. H. Wang and C. H. Brubaker, J. Mol. Catal., 75 (1992) 221-33. ##STR5## Y. Nishibayashi, K. Segawa, J. D. Singh, S. Fukuzawa, K. Ohe and S. Uemera, Organometallics, 15 (1996) 370-9.
A synthesis method is described hereinbelow that for the first time makes it possible to prepare chiral ferrocenyl ligands selectively having two different radicals in the 1,1'-position. Preferably the two different radicals are two different phosphine radicals or sulfur radicals or a sulfur radical and a phosphine radical. This makes it possible to adjust the electronic and steric properties of the chiral ferrocenyls according to the invention and of their metal complexes within a very wide range.
The invention relates to compounds of the formula ##STR6## wherein
R.sub.1 is C.sub.1 -C.sub.8 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl substituted by from 1 to 3 substituents selected from C.sub.1 -C.sub.4 alkyl and C.sub.1 -C.sub.4 alkoxy;
R.sub.a is --P(R.sub.10 R.sub.11) or --SR.sub.12 ;
R.sub.b is --P(R'.sub.10 R'.sub.11), --SR'.sub.12, --CH.dbd.NR.sub.12, --CH.sub.2 --NH--R.sub.12 or --CH.sub.2 --O--P(R.sub.10 R.sub.11);
R.sub.10 and R.sub.11 are each independently of the other C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 alkyl substituted by C.sub.1 -C.sub.4 alkoxy, C.sub.5 -C.sub.12 cycloalkyl or by phenyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, C.sub.5 -C.sub.12 cycloalkyl substituted by C.sub.1 -C.sub.4 alkyl or by C.sub.1 -C.sub.4 alkoxy, or phenyl substituted by from one to three substituents selected from C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, --SiR.sub.4 R.sub.5 R.sub.6, halogen, --SO.sub.3 M, --CO.sub.2 M, --PO.sub.3 M, --NR.sub.7 R.sub.8, --[.sup.+ NR.sub.7 R.sub.8 R.sub.9 ]X.sup.- and C.sub.1 -C.sub.5 fluoroalkyl; or
R.sub.10 and R.sub.11 together are C.sub.4 -C.sub.8 alkylene, C.sub.4 -C.sub.8 alkylene substituted by C.sub.1 -C.sub.4 alkyl or by phenyl, or annelated C.sub.4 -C.sub.8 alkylene;
R'.sub.10 and R'.sub.11 are each independently of the other as defined by R.sub.10 and R.sub.11, with the proviso that --P(R.sub.10 R.sub.11) is not identical to --P(R'.sub.10 R'.sub.11);
R.sub.12 is H, C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 alkyl substituted by C.sub.1 -C.sub.4 alkoxy, C.sub.5 -C.sub.12 cycloalkyl or by phenyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, C.sub.5 -C.sub.12 cycloalkyl substituted by C.sub.1 -C.sub.4 alkyl or by C.sub.1 -C.sub.4 alkoxy, or phenyl substituted by from one to three substituents

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