Process for enantioselective hydrogenation of the oxo C.dbd.O do

Details Process for enantioselective hydrogenation of the oxo C.dbd.O do Process for enantioselective hydrogenation of the oxo C.dbd.O do

1995-03-09

1997-03-25

Ivy, C. Warren

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

560 55, 560 56, 560126, 560129, 568799, 568832, 568861, C07D30732, C07C 3508, C07C 2700, C07C 6476

Patent

active

056146418

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

The present invention concerns a novel enantioselective catalytic hydrogenation process for the oxo C.dbd.O, or ketone, double bond. This novel process produces an enantiomerically pure or highly pure secondary alcohol from a ketone. It uses a neutral ruthenium complex.


PRIOR ART

Hydrogenation of the C.dbd.O carbonyl function to produce a primary alcohol which does not contain an asymmetrical carbon atom when the carbonyl function is constituted by a formyl group and to produce a secondary alcohol function containing an asymmetrical carbon atom when the carbonyl function is constituted by an oxo (i.e. ketone) group is known to occur via the following mechanisms: ##STR2##
Hydrogenation of a ketone C.dbd.O double bond generally produces a compound containing a secondary alcohol function which is constituted by a mixture of enantiomers. That mixture is then treated to isolate the enantiomer which is deemed to be important using a known method which is generally long and tedious. These treatments include chiral chromatography (especially HPLC) and fractionated crystallisation.
In order to overcome the problems associated with this type of isolation, ruthenium complexes, especially those containing acetate or halide groups, have been proposed for use as enantioselective hydrogenation catalysts for the ketone C.dbd.O carbonyl function; see, for example, POWEL et al., J. Chem. Soc., (1968), pp 159-161, R. NOYORI et al., J. Am. Chem. Soc., (1987), pp 5856-5858, M. KITAMURA et al., J. Am. Chem. Soc., (1988), 110, pp 629-631, and T IKARIYA et al., J. Chem. Soc., Chem. Comm., (1985), p 922.
The use of ruthenium based catalysts from the group of complexes known as "ionic", on the one hand, and "neutral", on the other hand, is known in the field of hydrogenation of ethylenically unsaturated organic compounds containing at least one aliphatic C.dbd.C double bond.
French patent application No 90 165 414 filed 28 Dec. 1992 (publication number FR-A-2 671 079, published 3 Jul. 1992) and the corresponding International application PCT/FR 91/01077 filed 27 Dec. 1991 describe catalysts for the catalytic hydrogenation of ethylenically unsaturated compounds, the catalysts being "neutral" ruthenium complexes in which: (i) two tertiary phosphine groups are bonded to the same Ru atom, the P atoms of said tertiary phosphine groups being bonded together by a chain containing at least two catenary atoms, and (ii) two allyl or methallyl residues are bonded to the same Ru atom.
The Ru complexes described in the above French patent application and international application are diallyl (diphosphino) ruthenium compounds which can be represented by the following formula I: ##STR3## where al represents an allyl group, atoms and which can contain one to four catenary heteroatoms selected from O, S, N and Si, C.sub.1 -C.sub.18 alkyl, C.sub.5 -C.sub.7 cycloalkyl or C.sub.6 -C.sub.12 aryl group.
The allyl groups al defined above include all allyl groups. The simplest and most economical are the allyl group itself with formula CH.sub.2 CH.dbd.CH.sub.2 and in particular the methallyl group with formula CH.sub.2 C(CH.sub.3).dbd.CH.sub.2, hereinafter abbreviated to "Met".


OBJECTS OF THE INVENTION

One object of the invention is to provide a novel catalytic hydrogenation process for the ketone C.dbd.O double bond without substantially affecting the carbonyl C.dbd.O group included in any carboxylic acid group --C(.dbd.O)--OH, carboxylate group --C(.dbd.O)--O-- or carboxamide group --C(.dbd.O)--NH-- which may be present in the ketone which is to be reduced to an alcohol.
A further object of the invention is to provide a novel catalytic hydrogenation process for the ketone C.dbd.O double bond which can produce optically active secondary alcohols in a yield greater than 85%, preferably greater than 90% and most preferably in the order of 99% to 100% with respect to the starting ketones, along with e.e of at least 35%.
In accordance with the invention, optically active secondary alcohols are prepared for use as intermediate co

REFERENCES:
patent: 4343741 (1982-08-01), Townsend et al.
patent: 5159093 (1992-10-01), Taketomi et al.
patent: 5274146 (1993-12-01), Ishizaki et al.
patent: 5286888 (1994-02-01), Sano et al.
patent: 5306834 (1994-04-01), Takaya et al.
patent: 5324861 (1994-06-01), Ishizaki et al.
patent: 5430191 (1995-07-01), Foricher et al.
patent: 5481008 (1996-01-01), Broger et al.

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