Catalytic asymmetric hydrogenation by some homogeneous and silica-bound μ-thiolato-μ-chlorodicarbonylbis- (neomenthyldiphenylphosphine) dirhodium complexes

TY - JOUR

T1 - Catalytic asymmetric hydrogenation by some homogeneous and silica-bound μ-thiolato-μ-chlorodicarbonylbis- (neomenthyldiphenylphosphine) dirhodium complexes

AU - Eisen, Moris

AU - Blum, Jochanan

AU - Schumann, Herbert

AU - Gorella, Boris

N1 - Funding Information: The authors thank the Deutsche Forschungsgemeinschaft (DFG), the Fonds der Chemischen Industrie and the Technical University of Berlin for financial support of this study, as well as Degussa, Hannau for a valuable gift of rhodium.

PY - 1989/11/15

Y1 - 1989/11/15

N2 - (+)-Dicarbonyl-μ-chloro[μ-(2-methyl-2-propanethiolato-S:S)]bis{[5-methyl-2-(1-methylethyl)cyclohexyl] diphenylphosphine}dirhodium (6a) and (+) - dicarbonyl-μ-chloro[μ-(2-triethoxysilyl)ethanethiolato-S:S]bis{[5-methyl-2-(1-methylethyl)cyclohexyl] diphenylphosphine}dirhodium (6b) were prepared by interaction of (+)-neomenthyldiphenylphosphine (3) with chlorodicarbonylrhodium dimer (2), followed by treatment of the product with the appropriate (alkylthio)trimethylsilane, 5. Complex 6b was immobilized by attachment to silica gel. Both the homogeneous and hybrid catalyts proved capable of promoting the asymmetric hydrogenation of prochiral unsaturated acids and esters. While the soluble complexes 6a and 6b led to the formation of dextro-rotatory products, the recyclable supported catalyst gave laevorotatory compounds.

AB - (+)-Dicarbonyl-μ-chloro[μ-(2-methyl-2-propanethiolato-S:S)]bis{[5-methyl-2-(1-methylethyl)cyclohexyl] diphenylphosphine}dirhodium (6a) and (+) - dicarbonyl-μ-chloro[μ-(2-triethoxysilyl)ethanethiolato-S:S]bis{[5-methyl-2-(1-methylethyl)cyclohexyl] diphenylphosphine}dirhodium (6b) were prepared by interaction of (+)-neomenthyldiphenylphosphine (3) with chlorodicarbonylrhodium dimer (2), followed by treatment of the product with the appropriate (alkylthio)trimethylsilane, 5. Complex 6b was immobilized by attachment to silica gel. Both the homogeneous and hybrid catalyts proved capable of promoting the asymmetric hydrogenation of prochiral unsaturated acids and esters. While the soluble complexes 6a and 6b led to the formation of dextro-rotatory products, the recyclable supported catalyst gave laevorotatory compounds.

UR - http://www.scopus.com/inward/record.url?scp=0024770562&partnerID=8YFLogxK

U2 - 10.1016/0304-5102(89)80196-8

DO - 10.1016/0304-5102(89)80196-8

M3 - 文章

AN - SCOPUS:0024770562

SN - 0304-5102

VL - 56

SP - 329

EP - 337

JO - Journal of Molecular Catalysis

JF - Journal of Molecular Catalysis

IS - 1-3

ER -