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Stereospecific Asymmetric N‑Heterocyclic Carbene (NHC)-Catalyzed Redox Synthesis of Trifluoromethyl Dihydropyranones and Mechanistic Insights

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journal contribution
posted on 20.09.2013, 00:00 by 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
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.