Direct catalytic asymmetric addition of allyl cyanide to ketones

Ryo Yazaki; Naoya Kumagai; Masakatsu Shibasaki

doi:10.1021/ja900001u

Direct catalytic asymmetric addition of allyl cyanide to ketones

J Am Chem Soc. 2009 Mar 11;131(9):3195-7. doi: 10.1021/ja900001u.

Authors

Ryo Yazaki¹, Naoya Kumagai, Masakatsu Shibasaki

Affiliation

¹ Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

PMID: 19215140
DOI: 10.1021/ja900001u

Abstract

A direct catalytic asymmetric addition of allyl cyanide to ketones with a bimetallic catalytic system comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]ClO(4)/LiOAr is described. Exclusive gamma-addition of allyl cyanide was observed, affording optically enriched tertiary alcohols bearing Z-configured alpha,beta-unsaturated nitriles. The reaction proceeded under proton-transfer conditions, utilizing soft Lewis acid/hard Brønsted base bifunctional catalysis. The applicability of the reaction to aromatic, heteroaromatic, and aliphatic ketones demonstrates its wide substrate generality.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Catalysis
Computer Simulation
Ketones / chemical synthesis*
Ketones / chemistry
Models, Chemical
Molecular Structure
Nitriles / chemistry*
Stereoisomerism

Substances

Ketones
Nitriles