Protonation of acyl anion equivalents generated from acylphosphonates: nonhydride access to the aldehyde oxidation state from the carboxylic acid oxidation state

Demir A. S., Reis O., Esiringu I., Reis B., Baris S.

TETRAHEDRON, vol.63, no.1, pp.160-165, 2007 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 63 Issue: 1
  • Publication Date: 2007
  • Doi Number: 10.1016/j.tet.2006.10.036
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.160-165
  • Keywords: acylphosphonates, cyanohydrin O-phosphates, acyl anion, rearrangements, carboxylic acids, PHOSPHONATE-PHOSPHATE REARRANGEMENT, ENANTIOSELECTIVE SYNTHESIS, CYANO-PHOSPHORYLATION, FACILE SYNTHESIS, ACYLSILANES, CONVENIENT, CATALYST, UMPOLUNG, KETONES
  • Middle East Technical University Affiliated: Yes

Abstract

Acylphosphonates, which are easily available from carboxylic acids, are potent acyl anion precursors and undergo cyanide ion promoted phosphonate-phosphate rearrangement to provide the corresponding acyl anion equivalents as reactive intermediates. The protonation of these acyl anion equivalents furnished cyanohydrin O-phosphates in good yields. For the high yield formation of cyanohydrin O-phosphates from arylphosphonates THF should be used and from alkylphosphonates DME was used. (c) 2006 Elsevier Ltd. All rights reserved.