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Aryloxide-facilitated catalyst turnover in enantioselective α,β-unsaturated acyl ammonium catalysis

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Anastassia Matviitsuk, Mark Greenhalgh, Diego Barrios Antunez, Alexandra Slawin, Andrew David Smith

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Abstract

A new general concept for α,β-unsaturated acyl ammonium catalysis is reported that uses p-nitrophenoxide release from an α,β-unsaturated p-nitrophenyl ester substrate to facilitate catalyst turnover. This method was used for the enantioselective isothiourea-catalyzed Michael addition of nitroalkanes to α,β-unsaturated p-nitrophenyl esters in generally good yield and with excellent enantioselectivity (27 examples, up to 79% yield, 99:1 er). Mechanistic studies identified rapid and reversible catalyst acylation by the α,β-unsaturated p-nitrophenyl ester, and a recently-reported variable time normalization kinetic analysis method was used to delineate the complex reaction kinetics.
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Original languageEnglish
JournalAngewandte Chemie International Edition
VolumeEarly View
Early online date25 Aug 2017
DOIs
StateE-pub ahead of print - 25 Aug 2017

    Research areas

  • Lewis base catalysis, α,β-unsaturated ammonium, Isothiourea, Aryloxide catalyst turnover, Kinetic and mechanistic analysis

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