Trans-RuH(eta1-BH4)(binap)(1,2-diamine): a Catalyst for Asymmetric Hydrogenation of Simple Ketones Under Base-free Conditions

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2002 Jun 6

PMID 12047151

Citations 19

Authors

Takeshi Ohkuma

Masatoshi Koizumi

Kilian Muniz

Gerhard Hilt

Chizuko Kabuto

Ryoji Noyori

Affiliations

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Abstract

Reaction of a chiral RuCl2(diphosphine)(1,2-diamine) complex and NaBH4 forms trans-RuH(eta1-BH4)(diphosphine)(1,2-diamine) quantitatively. The TolBINAP/DPEN Ru complex has been characterized by single crystal X-ray analysis as well as NMR and IR spectra. The new Ru complexes allow for asymmetric hydrogenation of simple ketones in 2-propanol without an additional strong base. Various base-sensitive ketones are convertible to chiral alcohols in a high enantiomeric purity with a substrate/catalyst ratio of up to 100 000 under mild conditions. Configurationally unstable 2-isopropyl- and 2-methoxycyclohexanone can be kinetically resolved with a high enantiomer discrimination. This procedure overcomes the drawback of an earlier method using RuCl2(diphosphine)(diamine) and an alkaline base, which sometimes causes undesired reactions such as ester exchange, epoxy-ring opening, beta-elimination, and polymerization of ketonic substrates.

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