Enantioselective polyene cyclization via organo-SOMO catalysis

Sebastian Rendler, David W.C. MacMillan

Research output: Contribution to journalArticlepeer-review

158 Scopus citations

Abstract

The first organocatalytic enantioselective radical polycyclization has been accomplished using singly occupied molecular orbital (SOMO) catalysis. The presented strategy relies on a selective single-electron oxidation of chiral enamines formed by condensation of polyenals with an imidazolidinone catalyst employing a suitable copper(II) oxidant. The reaction proceeds under mildly acidic conditions at room temperature and shows compatibility with an array of electron-poor as well as electron-rich functional groups. Upon termination by radical arylation followed by subsequent oxidation and rearomatization, a range of polycyclic aldehydes were accessed (12 examples, 54?77% yield, 85?93% ee). The enantioselective formation of up to six new carbocycles in a single catalyst-controlled cascade is described. Evidence for a radical-based cascade mechanism is indicated by a series of experimental results.

Original languageEnglish (US)
Pages (from-to)5027-5029
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number14
DOIs
StatePublished - Apr 14 2010

All Science Journal Classification (ASJC) codes

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

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