Enantioselective organocatalytic singly occupied molecular orbital activation: The enantioselective α-enolation of aldehydes

Hye Young Jang, Jun Bae Hong, David W.C. MacMillan

Research output: Contribution to journalArticle

228 Scopus citations

Abstract

The first enantioselective organocatalytic ∞-enolation of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Chiral secondary amines react with aldehydes to form transient enamines that undergo selective one-electron oxidation to generate electrophilic radical cations. These SOMO-activated radical cations are susceptible to attack by ketone-derived enol silanes, rendering ∞-substituted-γ-ketoaldehyde products with uniformly high levels of asymmetric induction. Wide latitude in both the aldehyde and enolsilane component is readily accommodated, allowing generic access to a diverse assortment of enantioenriched 1,4-dicarbonyl compounds. This report highlights the potential of SOMO catalysis to enable the development of entirely new classes of asymmetric reactions that have no traditional catalytic equivalents.

Original languageEnglish (US)
Pages (from-to)7004-7005
Number of pages2
JournalJournal of the American Chemical Society
Volume129
Issue number22
DOIs
StatePublished - Jun 6 2007

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Enantioselective organocatalytic singly occupied molecular orbital activation: The enantioselective α-enolation of aldehydes'. Together they form a unique fingerprint.

Cite this