Rationalization of an unusual solvent-induced inversion of enantiomeric excess in organocatalytic selenylation of aldehydes

Jordi Burés, Paul Dingwall, Alan Armstrong, Donna G. Blackmond

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

Abstract

An unusual solvent-induced inversion of the sense of enantioselectivity observed in the α-selenylation of aldehydes catalyzed by a diphenylprolinol silyl ether catalyst is correlated to the presence of intermediates formed subsequent to the highly selective C-Se bond-forming step in the catalytic cycle. This work provides support for a mechanistic concept for enamine catalysis and includes a general role for "downstream intermediates" in selectivity outcomes in organocatalysis.

Original languageEnglish
Pages (from-to)8700-8704
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number33
Early online date07 Jul 2014
DOIs
Publication statusPublished - 11 Aug 2014
Externally publishedYes

Keywords

  • enantioselectivity
  • kinetics
  • organocatalysis
  • reaction mechanisms
  • solvent effects

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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