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Issue 4, 2017
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Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1,4-addition/Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights

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Abstract

2-Hydroxydihydropyran-5-ones behave as excellent polyfunctional reagents able to react with enals through oxa-Michael/Michael process cascade under the combination of iminium and enamine catalysis. These racemic hemiacetalic compounds are used as unconventional O-pronucleophiles in the initial oxa-Michael reaction, also leading to the formation of a single stereoisomer under a dynamic kinetic resolution (DKR) process. Importantly, by using β-aryl or β-alkyl substituted α,β-unsaturated substrates as initial Michael acceptors either kinetically or thermodynamically controlled diastereoisomers were formed with high stereoselection through the careful selection of the reaction conditions. Finally, a complete experimental and computational study confirmed the initially proposed DKR process during the catalytic oxa-Michael/Michael cascade reaction and also explained the kinetic/thermodynamic pathway operating in each case.

Graphical abstract: Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1,4-addition/Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights

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Publication details

The article was received on 02 Jan 2017, accepted on 28 Jan 2017 and first published on 30 Jan 2017


Article type: Edge Article
DOI: 10.1039/C7SC00009J
Citation: Chem. Sci., 2017,8, 2904-2913
  • Open access: Creative Commons BY-NC license
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    Racemic hemiacetals as oxygen-centered pronucleophiles triggering cascade 1,4-addition/Michael reaction through dynamic kinetic resolution under iminium catalysis. Development and mechanistic insights

    A. Orue, U. Uria, D. Roca-López, I. Delso, E. Reyes, L. Carrillo, P. Merino and J. L. Vicario, Chem. Sci., 2017, 8, 2904
    DOI: 10.1039/C7SC00009J

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