Unanticipated Silyl Transfer in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis Using Silyl Nitronates

Anastassia Matviitsuk; Mark D. Greenhalgh; James E. Taylor; Xuan B. Nguyen; David B. Cordes; Alexandra M.Z. Slawin; David W. Lupton; Andrew D. Smith

doi:10.1021/acs.orglett.9b04404

Unanticipated Silyl Transfer in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis Using Silyl Nitronates

Anastassia Matviitsuk
, Mark D. Greenhalgh
, James E. Taylor
, Xuan B. Nguyen
, David B. Cordes
, Alexandra M.Z. Slawin
, David W. Lupton
, Andrew D. Smith

Department of Chemistry

University of St Andrews
Monash University

Research output: Contribution to journal › Article › peer-review

21 Citations (SciVal)

22 Downloads (Pure)

Abstract

The use of silyl nitronates is reported for the isothiourea-catalyzed synthesis of γ-nitro-substituted silyl esters containing up to two contiguous stereocenters in good yields with excellent enantioselectivities (up to 93% yield and 99:1 er). The serendipitously discovered formation of silyl ester products in this reaction demonstrates a novel platform for catalyst turnover in α,β-unsaturated acyl ammonium catalysis.

Original language	English
Pages (from-to)	335-339
Number of pages	5
Journal	Organic Letters
Volume	22
Issue number	1
Early online date	23 Dec 2019
DOIs	https://doi.org/10.1021/acs.orglett.9b04404
Publication status	Published - 3 Jan 2020

Funding

We thank the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007–2013), ERC Grant Agreement 279850 (A.D.S.), the EPSRC (EP/J018139/1, A.M.), and the Royal Society of Chemistry (Researcher Mobility Grant). A.D.S. thanks the Royal Society for a Wolfson Research Merit Award. D.W.L. thanks the Australian Research Council for a Discovery Award (DP170103567). We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University.

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.9b04404

ITU Silyl Nitronates_Revised Manuscript_Accepted
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abstract = "The use of silyl nitronates is reported for the isothiourea-catalyzed synthesis of γ-nitro-substituted silyl esters containing up to two contiguous stereocenters in good yields with excellent enantioselectivities (up to 93\% yield and 99:1 er). The serendipitously discovered formation of silyl ester products in this reaction demonstrates a novel platform for catalyst turnover in α,β-unsaturated acyl ammonium catalysis.",

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AU - Nguyen, Xuan B.

AU - Cordes, David B.

AU - Slawin, Alexandra M.Z.

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AU - Smith, Andrew D.

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AB - The use of silyl nitronates is reported for the isothiourea-catalyzed synthesis of γ-nitro-substituted silyl esters containing up to two contiguous stereocenters in good yields with excellent enantioselectivities (up to 93% yield and 99:1 er). The serendipitously discovered formation of silyl ester products in this reaction demonstrates a novel platform for catalyst turnover in α,β-unsaturated acyl ammonium catalysis.

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Unanticipated Silyl Transfer in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis Using Silyl Nitronates

Abstract

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ASJC Scopus subject areas

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