Enantioselective α-arylation of aldehydes via organo-SOMO catalysis. An ortho-selective arylation reaction based on an open-shell pathway

Jay C. Conrad, Jongrock Kong, Brian N. Laforteza, David W.C. MacMillan

Research output: Contribution to journalArticle

188 Scopus citations

Abstract

(Chemical Equation Presented) The intramolecular-arylation of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Selective oxidation of chiral enamines (formed by the condensation of an aldehyde and a secondary amine catalyst) leads to the formation of a 3π-electron radical species. These chiral SOMO-activated radical cations undergo enantioselective reaction with an array of pendent electron-rich aromatics and heterocycles thus efficiently providing cyclic α-aryl aldehyde products (10 examples: ≥70% yield and ≥90% ee). In accordance with our radical mechanism, when there is a choice between arylation at the ortho or para position of anisole substrates, we find that arylation proceeds selectively at the ortho position.

Original languageEnglish (US)
Pages (from-to)11640-11641
Number of pages2
JournalJournal of the American Chemical Society
Volume131
Issue number33
DOIs
StatePublished - Aug 26 2009

All Science Journal Classification (ASJC) codes

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

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