Direct catalytic asymmetric addition of allylic cyanides to ketoimines

Ryo Yazaki; Tatsuya Nitabaru; Naoya Kumagai; Masakatsu Shibasaki

doi:10.1021/ja806572b

Direct catalytic asymmetric addition of allylic cyanides to ketoimines

J Am Chem Soc. 2008 Nov 5;130(44):14477-9. doi: 10.1021/ja806572b. Epub 2008 Oct 10.

Authors

Ryo Yazaki¹, Tatsuya Nitabaru, 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: 18844357
DOI: 10.1021/ja806572b

Abstract

Direct catalytic asymmetric addition of allylic cyanides to N-diphenylphosphinoyl ketoimines with a bimetallic catalytic system comprising Ph-BPE/[Cu(CH3CN)4]ClO4/LiOAr is described. Intermediary alpha-adducts readily isomerized to afford synthetically useful alpha,beta-unsaturated nitriles bearing an optically active tetrasubstituted carbon. Applicability to aromatic, heteroaromatic, and aliphatic ketoimines exemplifies wide substrate generality. Transformation of the product into densely functionalized material showcases the utility of the present protocol.

Publication types

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

MeSH terms

Catalysis
Imines / chemical synthesis
Imines / chemistry*
Ketones / chemical synthesis
Ketones / chemistry*
Nitriles / chemical synthesis*
Nitriles / chemistry
Organophosphorus Compounds / chemistry

Substances

Imines
Ketones
Nitriles
Organophosphorus Compounds
allyl cyanide