Copper-Catalyzed Electrophilic Amination of Organozinc Nucleophiles:  Documentation of O-Benzoyl Hydroxylamines as Broadly Useful R2N(+) and RHN(+) Synthons

Ashley M. Berman and Jeffrey S. Johnson*
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290
J. Org. Chem., 2006, 71 (1), pp 219–224
DOI: 10.1021/jo051999h
Publication Date (Web): December 2, 2005
Copyright © 2006 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.

, jsj@unc.edu

Abstract

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This paper details new copper-catalyzed electrophilic amination reactions of diorganozinc reagents using O-benzoyl hydroxylamines as electrophilic nitrogen sources that may be accessed in one step. Simple and functionalized aryl, heteroaryl-, benzyl, n-alkyl, sec-alkyl, and tert-alkyl nucleophiles couple with R2NOC(O)Ph and RHNOC(O)Ph reagents in the presence of catalytic quantities of copper salts to provide tertiary and secondary amines, respectively, in generally good yields. In many cases, the product may be isolated analytically pure after a simple extractive workup. The amination process is shown to tolerate a significant degree of steric demand. The amination of nominally unreactive Caryl−H bonds via a sequential directed ortho metalation/transmetalation/catalytic amination reaction sequence is detailed. The direct Cu-catalyzed amination of Grignard reagents using cocatalysis by ZnCl2 is described.

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History

  • Published In Issue January 06, 2006
  • Received September 23, 2005

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