Catalytic enantioselective construction of all-carbon quaternary stereocenters: synthetic and mechanistic studies of the C-acylation of silyl ketene acetals

J Am Chem Soc. 2005 Apr 20;127(15):5604-7. doi: 10.1021/ja043832w.

Abstract

With the aid of an appropriate chiral catalyst, acyclic silyl ketene acetals react with anhydrides to furnish 1,3-dicarbonyl compounds that bear all-carbon quaternary stereocenters in good ee and yield. Mechanistic studies provide strong support for a catalytic cycle that involves activation of both the electrophile (anhydride --> acylpyridinium) and the nucleophile (silyl ketene acetal --> enolate).

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Acetals / chemistry*
  • Acylation
  • Anhydrides / chemistry
  • Catalysis
  • Ethylenes / chemistry*
  • Ketones / chemistry*
  • Pyridinium Compounds / chemistry
  • Silanes / chemistry*
  • Stereoisomerism

Substances

  • Acetals
  • Anhydrides
  • Ethylenes
  • Ketones
  • Pyridinium Compounds
  • Silanes
  • ketene