Synthesis of Tertiary β-Hydroxy Amides by Enolate Additions to Acylsilanes

Robert B. Lettan II, Troy E. Reynolds, Chris V. Galliford, and Karl A. Scheidt*
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208
J. Am. Chem. Soc., 2006, 128 (49), pp 15566–15567
DOI: 10.1021/ja065605v
Publication Date (Web): November 11, 2006
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.

, scheidt@northwestern.edu

Abstract

Abstract Image

The synthesis of tertiary β-hydroxy amides from acylsilanes, acetamides, and electrophiles is described. The addition of amide enolates to acylsilanes generates β-silyloxy homoenolate reactivity by undergoing a 1,2-Brook rearrangement. These unique nucleophiles formed in situ can then undergo smooth addition to alkyl halides, aldehydes, and ketones. Enolates derived from amides are crucial for the success of this process since ketone enolates suffer from internal return of the β-carbanion onto the carbonyl carbon. The use of optically active amide enolates delivers β-hydroxy amide products with good levels of diastereoselectivity (≥10:1).

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History

  • Published In Issue December 13, 2006
  • Received August 2, 2006

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