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

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

Research output: Contribution to journalArticlepeer-review

24 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)12450-12455
Number of pages6
JournalAngewandte Chemie
Volume129
Issue number40
Early online date25 Aug 2017
DOIs
Publication statusPublished - 25 Sept 2017

Keywords

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

Fingerprint

Dive into the research topics of 'Aryloxide-facilitated catalyst turnover in enantioselective α,β-unsaturated acyl ammonium catalysis'. Together they form a unique fingerprint.

Cite this