A General, Highly Enantioselective Method for the Synthesis of d and l α-Amino Acids and Allylic Amines

Young K. Chen, Alice E. Lurain, and Patrick J. Walsh*
Contribution from the P. Roy and Diane T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323
J. Am. Chem. Soc., 2002, 124 (41), pp 12225–12231
DOI: 10.1021/ja027271p
Publication Date (Web): September 24, 2002
Copyright © 2002 American Chemical Society
*

 To whom correspondence should be addressed. E-mail:  pwalsh@sas.upenn.edu. Phone:  (215) 573-2875. Fax:  (215) 573-6743.

Abstract

Abstract Image

Catalytic and enantioselective synthesis of amino acids is a subject of intense interest in the field of asymmetric catalysis. Traditionally, researchers have concentrated their efforts largely on the design and discovery of enantiopure catalysts for the Strecker reaction, alkylation of tert-butyl gylcinate-benzophenone, electrophilic amination of carbonyl compounds, and hydrogenation of N-acyl-aminoacrylic acid; however, the scope of these reactions is limited. In this paper, we report on a different approach to amino acids based on an expeditious route to enantiopure allylic amines. A highly enantioselective and catalytic vinylation of aldehydes leads to allylic alcohols that are then transformed to the allylic amines via Overman's [3,3]-sigmatropic rearrangement of imidates. Oxidative cleavage of the allylic amines furnishes the amino acids in good yields and excellent ee's. The scope and utility of this method are demonstrated by the synthesis of challenging allylic amines and their subsequent transformation to valuable nonproteinogenic amino acids, including both d and l configured (1-adamantyl)glycine.

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History

  • Published In Issue October 16, 2002
  • Received June 12, 2002

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