Org. Lett., 5 (11), 1809 -1812, 2003. 10.1021/ol0271786 S1523-7060(02)07178-X
Web Release Date: May 8, 2003

Copyright © 2003 American Chemical Society

Catalytic Asymmetric Rearrangement of Allylic N-Aryl Trifluoroacetimidates. A Useful Method for Transforming Prochiral Allylic Alcohols to Chiral Allylic Amines

Larry E. Overman,* Carolyn E. Owen, and Mary M. Pavan

Department of Chemistry, University of California, Irvine, 516 Rowland Hall, Irvine, California 92697-2025

Christopher J. Richards*

Department of Chemistry, Queen Mary, University of London, Mile End Road, London E1 4NS, U.K.

leoverma@uci.edu

Received October 25, 2002

Revised April 22, 2003

Abstract:

A useful method for the conversion of prochiral allylic alcohols to chiral allylic amines of high enantiopurity is reported. N-(4-Methoxyphenyl)trifluoroacetimidates are excellent substrates for the palladium(II)-catalyzed allylic imidate rearrangement as the allylic trifluoroacetamide products can be deprotected in two steps to provide chiral nonracemic allylic amines. Di--chlorobis[(5-(S)-(pR)-2-(2'-(4'-isopropyl))oxazolinylcyclopentadienyl,1-C,3'-N))(4-tetraphenylcyclobutadiene)cobalt]dipalladium (6a, COP-Cl) is a superior catalyst because it does not require activation with silver salts and provides rearranged allylic trifluoroacetamides in good yields and high enantiomeric purities.

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