Process for producing optically active .gamma.-hydroxyketones
AssigneeTakasago International Corporation
InventorsSeiji Watanabe, Shigeru Mitsuhashi, Hidenori Kumobayashi
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Abstract
Disclosed herein is a process for producing a .gamma.-hydroxyketone (2), which comprises asymmetrically hydrogenating a .gamma.-diketone (1) in the presence of a ruthenium-optically active phosphine complex as a catalyst ##STR1## wherein R.sup.1 and R.sup.2 mean individually an alkyl or phenyl group which may have a substituent group. According to the invention, optically active .gamma.-hydroxyketones useful in synthesizing optically active moiety in, biodegradable polymers, perfumes, intermediates for synthesizing medicines and the like can be efficiently prepared.
Claims14
A process for producing a .gamma.-hydroxyketone having the formula (2) ##STR6## wherein R.sup.1 and R.sup.2 are, individually, C.sub.1-8 -alkyl, C.sub.1-8 alkyl substituted with phenyl, halogen or alkoxy groups, phenyl, or phenyl substituted with halogen, lower alkyl or lower alkoxy groups, comprising:
- asymmetrically hydrogenating a .gamma.-diketone having the formula (1) ##STR7## wherein R.sup.1 and R.sup.2 have the same meaning as defined above, in the presence of a ruthenium-optically active phosphine complex catalyst, said catalyst having the formula (4)
- {RuA.sub.k (B).sub.m (BIPHOS)}Yn (4)
- wherein BIPHOS is a tertiary phosphine having the formula (a), (b) or (c) ##STR8## wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14, individually, are a hydrogen atom, a halogen atom, a C.sub.1-4 alkyl group or a C.sub.1-4 alkoxy group, A is a halogen atom, B is acetonitrile, benzene or methylbenzoate, Y is a halogen atom, ClO.sub.4, PF.sub.6, BPh.sub.4 or BF.sub.4 ;
- where k, m and n are 1,1 and 1, respectively, when B is benzene or methylbenzoate;
- m and n are 2 and 1, respectively, when B is acetonitrile and k is 1;
- and m and n are 4 and 2, respectively, when B is acetonitrile and k is 0;
- or a catalyst having the formula (5)
- {RuI(p-cymene) (BIPHOS)}I.sub.3 ( 5)
- wherein BIPHOS is a tertiary phosphine having said formula (a), (b) or (c) defined above;
- or a catalyst having the formula (6)
- Ru(OCO-R.sup.15).sub.2 (BIPHOS) (6)
- wherein R.sup.15 is a hydrogen atom, trifluoromethyl, or a lower alkyl group, and BIPHOS is a tertiary phosphine having said formula (b) or (c) defined above,
- or a catalyst having formula (3)
- Ru.sub.x H.sub.y Cl.sub.z (BIPHOS).sub.2 (S).sub.p ( 3)
- wherein BIPHOS is a tertiary phosphine having said formula (b) or (c), (S) is a tertiary amine;
- where x, z and p are 2,4 are 1, respectively, when y is zero;
- and x, z and p are 1,1 and 0, respectively, when y is 1.
Dependencies are inferred from the claim text.