Stereospecific asymmetric N-heterocyclic carbene (NHC)-catalyzed redox synthesis of trifluoromethyl dihydropyranones and mechanistic insights

Alyn T. Davies, James E. Taylor, James Douglas, Christopher J. Collett, Louis C. Morrill, Charlene Fallan, Alexandra M.Z. Slawin, Gwydion Churchill, Andrew D. Smith

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47 Citations (Scopus)

Abstract

N-Heterocyclic carbene (NHC)-catalyzed redox asymmetric hetero-Diels-Alder reactions of α-aroyloxyaldehydes with β-trifluoromethyl enones generates synthetically useful dihydropyranones containing a stereogenic trifluoromethyl substituent in good yields (up to 81%) and excellent diastereoselectivity and enantioselectivity (up to >95:5 dr and >99% ee). The process is stereospecific, with use of either (E)- or (Z)-β- trifluoromethyl enones forming syn- or anti-dihydropyranone products, respectively. Mechanistic studies through in situ kinetic analysis of the reaction reveal key differences in reactivity between chiral NHC precursor 1 and an achiral NHC precursor.

Original languageEnglish
Pages (from-to)9243-9257
Number of pages15
JournalJournal of Organic Chemistry
Volume78
Issue number18
Early online date19 Aug 2013
DOIs
Publication statusPublished - 20 Sep 2013

ASJC Scopus subject areas

  • Organic Chemistry

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    Davies, A. T., Taylor, J. E., Douglas, J., Collett, C. J., Morrill, L. C., Fallan, C., Slawin, A. M. Z., Churchill, G., & Smith, A. D. (2013). Stereospecific asymmetric N-heterocyclic carbene (NHC)-catalyzed redox synthesis of trifluoromethyl dihydropyranones and mechanistic insights. Journal of Organic Chemistry, 78(18), 9243-9257. https://doi.org/10.1021/jo401433q