Oxidatively Intercepting Heck Intermediates:  Pd-Catalyzed 1,2- and 1,1-Arylhalogenation of Alkenes

Dipannita Kalyani and Melanie S. Sanford*
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109
J. Am. Chem. Soc., 2008, 130 (7), pp 2150–2151
DOI: 10.1021/ja0782798
Publication Date (Web): January 30, 2008
Copyright © 2008 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.

, mssanfor@umich.edu

Abstract

Abstract Image

This communication describes the development of two Pd-catalyzed reactions for the arylchlorination of diverse α-olefins by oxidatively intercepting Heck intermediates. Depending on the nature of the oxidant and the reaction conditions, these transformations can afford synthetically useful 1,1- or 1,2-arylchlorinated products in good yields and with good to excellent selectivities. Preliminary mechanistic investigations show that the selectivity of these reactions can be rationally tuned (i) by controlling the relative rates of oxidative functionalization versus β-hydride elimination from equilibrating PdII−alkyl species and (ii) by π-benzyl stabilization of Pd intermediates.

View: Full Text HTML | Hi-Res PDF | PDF w/ Links

Tools

History

  • Published In Issue February 20, 2008
  • Received October 30, 2007

Recommend & Share

Related Content

Other ACS content by these authors: