Direct, Catalytic Hydroaminoalkylation of Unactivated Olefins with N-Alkyl Arylamines

Seth B. Herzon and John F. Hartwig*
Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801
J. Am. Chem. Soc., 2007, 129 (21), pp 6690–6691
DOI: 10.1021/ja0718366
Publication Date (Web): May 3, 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.

, jhartwig@uiuc.edu

Abstract

Abstract Image

A tantalum-catalyzed addition of N-alkyl arylamine α-C−H bonds across olefins is reported. These reactions occur with mono- and 2,2-disubstituted olefins to form the branched insertion products in high yield and regioselectivity. The reactions encompass additions of the α-C−H bonds of cyclic and acyclic amines, as well as intramolecular additions. NMR studies indicate that the starting homoleptic, Ta(NMe2)5 precatalyst converts to bis- and tris(N-methylanilide) complexes (among others) in solution. Deuterium-labeling studies suggest that reversible ortho-metalation of the arene substituent occurs under the reaction conditions. However, several experiments imply that this ortho-metalation does not lie on the reaction pathway. Instead, these complexes are proposed to eliminate amine to form N-aryl imine complexes, which insert olefins into the Ta−C bond and undergo protonolysis to regenerate the active catalyst and eliminate the addition product.

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History

  • Published In Issue May 30, 2007
  • Received March 15, 2007

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