Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1999-03-24
2000-12-26
Vollano, Jean F
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564150, 564318, 546134, 568814, 568880, 568308, 568361, C07C21143, C07C 4904, C07C 4912
Patent
active
061662577
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to a process for the asymmetric hydrogenation of a ketonic compound and derivative.
The invention relates to the use of optically active metal complexes as catalysts for the asymmetric hydrogenation of a ketonic compound and derivative.
French patent application no. 94/15757 and PCT/FR95/01716 describe novel optically active diphosphines of bis[1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene] of the following formulae: ##STR2##
The novel phosphines are obtained by a process for resolving the racemic mixture of bis[1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene], which consists in reacting it with a palladium or platinum complex as a chiral auxiliary, in an organic solvent, to form diastereoisomeric complexes, and then resolving said optically pure complexes.
The mixture of the two starting diastereoisomers (on the one hand a meso complex and on the other hand a racemic complex) can be obtained according to the teaching described by F. Mathey et al. in Bull. Soc. Chim. Fr. 129, pp. 1-8 (1992).
In the process of the invention described in FR no. 94/15757, the racemic mixture of bis[1-phospha-2,3-diphenyl-4,5-dimethylnorbornadiene] is resolved by being reacted with a palladium or platinum complex as a chiral auxiliary.
It is possible to use a palladium complex. This type of chiral auxiliary is widely described in the literature, especially by Sei Otsuka et al. in Journal of the American Chemical Society 93, p. 4301 (1971).
It is also possible to use a platinum complex and reference may be made more particularly to the work of A.C. Cope [Journal of the American Chemical Society 90, p. 909 (1968)].
More particularly, the chiral complex used has general formula (VII): ##STR3## in which: M is palladium and/or platinum; having from 1 to 10 carbon atoms or a cycloalkyl radical having from 3 to 10 carbon atoms; atom; benzene ring can together form a ring having from 5 to 7 carbon atoms.
More preferably, the complex used has the above-mentioned formula in which R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are a hydrogen atom or a methyl radical, X is a chlorine atom and n is equal to 0.
If n is equal to 2, two radicals R form a benzene ring.
The following may be mentioned as a more specific example of a palladium complex suitable for the present invention, arbitrarily obtained from (R)-(+)- or (S)-(-)-N,N-dimethylphenylethylamine: ##STR4##
The amount of complex of the above-mentioned metals, expressed in terms of metal, is generally 0.5 to 1 metal atom per phosphorus atom.
An organic solvent which solubilizes all the reactants is used. It must be inert towards the diphosphine.
The following may be mentioned as non-limiting examples of solvents which are suitable in the process of the invention: pentane, hexane, heptane, octane, isooctane, nonane, decane, undecane, tetradecane, petroleum ether and cyclohexane; and aromatic hydrocarbons such as especially benzene, toluene, xylenes, ethylbenzene, diethylbenzenes, trimethylbenzenes, cumene, pseudocumene and petroleum cuts consisting of a mixture of alkylbenzenes, especially cuts of the Solvesso.RTM. type; and hydrocarbons such as especially trichloromethane and tetrachloroethylene; and partially chlorinated hydrocarbons such as dichloromethane, dichloroethane, tetrachloroethane, trichloroethylene, 1-chlorobutane, 1,2-dichlorobutane, monochlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene or mixtures of different chlorobenzenes.
Among all these solvents, benzene and toluene are preferred.
The concentration of the diphosphine in the reaction solvent is preferably between 0.05 and 1 mol/liter and particularly preferably between 0.05 and 0.2 mol/liter.
The separation is advantageously performed at room temperature, generally between 15.degree. C. and 25.degree. C.
It preferably takes place under a controlled atmosphere of inert gases. It is possible to establish an atmosphere of rare gases, preferably argon, but it is more economic to use nitrogen.
This gives a mixture of complexes of palladium or platinum and diphosphine co
REFERENCES:
patent: 3636091 (1972-01-01), Mason
patent: 5426223 (1995-06-01), Burk
patent: 5516944 (1996-05-01), Broger
patent: 5783738 (1998-07-01), Mathey
patent: 5801263 (1998-09-01), Seitz
patent: 5874600 (1999-02-01), Rautenstrauch
A. Breque et al, "The use of 1-phosphanorbornadienes with chiral phosphorus at the bridgehead in catalytic asymmetric hydrogenation of dehydroaminoacids", New Journal of Chemistry, vol. 13, No. 4/5, 1989, pp. 369-374, XP000618266, see p. 370.
Mathey Francois
Mercier Francois
Robin Frederic
Spagnol Michel
Rhodia Chimie
Vollano Jean F
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