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

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

doi:10.1002/ange.201706402

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

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.

Original language	English
Pages (from-to)	12450-12455
Number of pages	6
Journal	Angewandte Chemie
Volume	129
Issue number	40
Early online date	25 Aug 2017
DOIs	https://doi.org/10.1002/ange.201706402
Publication status	Published - 25 Sept 2017

Keywords

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

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10.1002/ange.201706402Licence: CC BY

Matviitsuk_2017_Aryloxide-facilitatedCatalyst_CC
© 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 964 KBLicence: CC BY

RS Wolfson Merit Award: Developing Catalysis Research: New Reaction Discoveries and Practical Applications
Smith, A. D. (PI)
The Royal Society
1/01/15 → 31/12/19
Project: Fellowship
Clean catalysis for sustainable develop: Clean catalysis for sustainable development
Kamer, P. C. J. (PI)
EPSRC
1/11/12 → 31/10/17
Project: Standard
ERC Starting Grant EnolCat: Emulating nature: Reaction diversity and understanding through asymmetric catalysis
Smith, A. D. (PI)
European Commission
1/10/11 → 30/06/17
Project: Standard

Andrew David Smith
- ads10st-andrews.acuk
- School of Chemistry - Professor, Director of Research
- Biomedical Sciences Research Complex
- EaSTCHEM
Person: Academic

Data underpinning "Aryloxide-Facilitated Catalyst Turnover in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis"
Matviitsuk, A. (Creator), Greenhalgh, M. D. (Creator), Barrios Antunez, D. J. (Creator), Slawin, A. M. Z. (Creator) & Smith, A. D. (Creator), University of St Andrews, 9 Aug 2017
DOI: 10.17630/421487e5-d537-4fc8-b067-b6dd664c20d3
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title = "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.",

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

author = "Anastassia Matviitsuk and Mark Greenhalgh and {Barrios Antunez}, Diego and Alexandra Slawin and Smith, {Andrew David}",

note = "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.",

year = "2017",

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doi = "10.1002/ange.201706402",

language = "English",

volume = "129",

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T1 - Aryloxide-facilitated catalyst turnover in enantioselective α,β-unsaturated acyl ammonium catalysis

AU - Matviitsuk, Anastassia

AU - Greenhalgh, Mark

AU - Barrios Antunez, Diego

AU - Slawin, Alexandra

AU - Smith, Andrew David

N1 - 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.

PY - 2017/9/25

Y1 - 2017/9/25

N2 - 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.

AB - 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.

KW - Lewis base catalysis

KW - α,β-unsaturated ammonium

KW - Isothiourea

KW - Aryloxide catalyst turnover

KW - Kinetic and mechanistic analysis

U2 - 10.1002/ange.201706402

DO - 10.1002/ange.201706402

M3 - Article

SN - 0044-8249

VL - 129

SP - 12450

EP - 12455

JO - Angewandte Chemie

JF - Angewandte Chemie

IS - 40

ER -

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

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Projects

RS Wolfson Merit Award: Developing Catalysis Research: New Reaction Discoveries and Practical Applications

Clean catalysis for sustainable develop: Clean catalysis for sustainable development

ERC Starting Grant EnolCat: Emulating nature: Reaction diversity and understanding through asymmetric catalysis

Profiles

Andrew David Smith

Datasets

Data underpinning "Aryloxide-Facilitated Catalyst Turnover in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis"

Cite this