syn-1,2-Amino Alcohols via Diastereoselective Allylic C−H Amination

Kenneth J. Fraunhoffer and M. Christina White*
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801
J. Am. Chem. Soc., 2007, 129 (23), pp 7274–7276
DOI: 10.1021/ja071905g
Publication Date (Web): May 22, 2007
Copyright © 2007 American Chemical Society
*

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

, white@scs.uiuc.edu

Abstract

Abstract Image

A novel Pd/sulfoxide catalyzed diastereoselective allylic C−H amination reaction of chiral homoallylic N-tosyl carbamates is reported. Densely oxygenated α-olefin substrates with multiple stereogenic centers undergo allylic C−H amination in excellent yields and with diastereoselectivities that are controlled by the stereocenter that bears the N-tosyl carbamate. Streamlined routes to stereochemically defined anti-oxazolidinones that can be further elaborated to medicinally and biologically relevant 1,2-amino alcohols are also demonstrated. Evidence is provided that this reaction proceeds via a Pd/sulfoxide-mediated allylic C−H cleavage to form a π-allylPd intermediate followed by Pd(II) counterion-assisted deprotonation of the nitrogen nucleophile to effect functionalization.

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History

  • Published In Issue June 13, 2007
  • Received March 22, 2007

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