Volume 38, Issue 4 pp. 495-497
Communication

Conformationally Flexible Biphenyl-phosphane Ligands for Ru-Catalyzed Enantioselective Hydrogenation

Koichi Mikami

Koichi Mikami

Department of Chemical Technology, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152–8552 (Japan), Fax: (+81) 3-5734-2776

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Toshinobu Korenaga

Toshinobu Korenaga

Department of Chemical Technology, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152–8552 (Japan), Fax: (+81) 3-5734-2776

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Masahiro Terada

Masahiro Terada

Department of Chemical Technology, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152–8552 (Japan), Fax: (+81) 3-5734-2776

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Takeshi Ohkuma

Takeshi Ohkuma

Department of Chemistry and Molecular Chirality, Research Unit, Nagoya University, Chikusa, Nagoya 464–8602 (Japan), Fax: (+81) 52-783-4177

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Trang Pham

Trang Pham

Department of Chemistry and Molecular Chirality, Research Unit, Nagoya University, Chikusa, Nagoya 464–8602 (Japan), Fax: (+81) 52-783-4177

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Ryoji Noyori

Ryoji Noyori

Department of Chemistry and Molecular Chirality, Research Unit, Nagoya University, Chikusa, Nagoya 464–8602 (Japan), Fax: (+81) 52-783-4177

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Abstract

Stereomutation of a BIPHEP/RuCl2/diamine complex (shown schematically) is possible because of the conformational flexibilty of BIPHEP ligands. The result is an asymmetric activation in the Ru-catalyzed hydrogenation of carbonyl compounds to optically active alcohols. Whereas a racemic BINAP/RuCl2 complex with a chiral diamine activator gives a 1:1 mixture of two diastereomers, unequal amounts of the diastereomers can be produced from a BIPHEP/RuCl2 complex and a chiral diamine. Ar=3,5-dimethylphenyl, BINAP=2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl, BIPHEP=2,2′-bis(diarylphosphanyl)biphenyl.

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