Aryloxide-facilitated catalyst turnover in enantioselective α,β-unsaturated acyl ammonium catalysis
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.
Citation
Matviitsuk , A , Greenhalgh , M , Barrios Antunez , D , Slawin , A & Smith , A D 2017 , ' Aryloxide-facilitated catalyst turnover in enantioselective α,β-unsaturated acyl ammonium catalysis ' , Angewandte Chemie , vol. 129 , no. 40 , pp. 12450-12455 . https://doi.org/10.1002/ange.201706402
Publication
Angewandte Chemie
Status
Peer reviewed
ISSN
0044-8249Type
Journal article
Description
The authors thank the European Research Council under the European Union's Seventh Framework Programme (FP7/2007-2013) ERC grant agreement no. 279850 (A.D.S) and the EPSRC (EP/J018139/1, A.M.) for funding. A.D.S. thanks the Royal Society for a Wolfson Research Merit Award.Collections
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