Unanticipated silyl transfer in enantioselective α,β-unsaturated acyl ammonium catalysis using silyl nitronates

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

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

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
Journal	Organic Letters
Volume	Article ASAP
Early online date	23 Dec 2019
DOIs	https://doi.org/10.1021/acs.orglett.9b04404
Publication status	E-pub ahead of print - 23 Dec 2019

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Matviitsuk_2019_OL_Silyltransfer_AAM
Copyright © 2019 American Chemical Society. his work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.orglett.9b04404
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RS Wolfson Merit Award: Developing Catalysis Research: New Reaction Discoveries and Practical Applications
Smith, A. (PI)
The Royal Society
1/01/15 → 31/12/19
Project: Fellowship
Clean catalysis for sustainable develop: Clean catalysis for sustainable development
Smith, A. (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. (PI)
Joint Research Centre European Commission
1/10/11 → 30/06/17
Project: Standard

Data underpinning "Silyl Transfer in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis using Silyl Nitronates"
Smith, A. D. (Creator), Greenhalgh, M. D. (Owner) & Slawin, A. M. Z. (Owner), University of St Andrews, 31 Oct 2019
DOI: 10.17630/987798e4-e872-4007-bc92-931c73232a6b
Dataset

File
A C=O•••isothiouronium interaction dictates enantiodiscrimination in acylative kinetic resolution of tertiary heterocyclic alcohols (dataset 2)
Greenhalgh, M. D. (Creator), Smith, S. (Creator), Walden, D. M. (Creator), Taylor, J. E. (Creator), Brice, Z. (Creator), Robinson, E. (Creator), Fallan, C. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator), Richardson, H. C. (Creator), Grove, M. A. (Creator), Ha-Yeon Cheong, P. (Creator) & Smith, A. D. (Creator), Cambridge Crystallographic Data Centre, 2017
https://dx.doi.org/10.5517/ccdc.csd.cc1pq5k4 and one more link, https://dx.doi.org/10.5517/ccdc.csd.cc1pq5l5 (show fewer)
Dataset

Cite this

@article{729939de17b742b9b0c52802860c1b57,

title = "Unanticipated silyl transfer in enantioselective α,β-unsaturated acyl ammonium catalysis using silyl nitronates",

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.",

author = "Anastassia Matviitsuk and Greenhalgh, \{Mark David\} and Taylor, \{James E.\} and Nguyen, \{Xuan B.\} and Cordes, \{David Bradford\} and Slawin, \{Alexandra M. Z.\} and Lupton, \{David W.\} and Smith, \{Andrew D.\}",

note = "We thank the European Research Council under the European Union{\textquoteright}s Seventh Framework Programme (FP7/2007{\textendash}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.",

year = "2019",

month = dec,

day = "23",

doi = "10.1021/acs.orglett.9b04404",

language = "English",

volume = "Article ASAP",

journal = "Organic Letters",

issn = "1523-7060",

publisher = "American Chemical Society (ACS)",

}

TY - JOUR

T1 - Unanticipated silyl transfer in enantioselective α,β-unsaturated acyl ammonium catalysis using silyl nitronates

AU - Matviitsuk, Anastassia

AU - Greenhalgh, Mark David

AU - Taylor, James E.

AU - Nguyen, Xuan B.

AU - Cordes, David Bradford

AU - Slawin, Alexandra M. Z.

AU - Lupton, David W.

AU - Smith, Andrew D.

N1 - 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.

PY - 2019/12/23

Y1 - 2019/12/23

N2 - 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.

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.

U2 - 10.1021/acs.orglett.9b04404

DO - 10.1021/acs.orglett.9b04404

M3 - Article

SN - 1523-7060

VL - Article ASAP

JO - Organic Letters

JF - Organic Letters

ER -

Unanticipated silyl transfer in enantioselective α,β-unsaturated acyl ammonium catalysis using silyl nitronates

Abstract

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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

Datasets

Data underpinning "Silyl Transfer in Enantioselective α,β-Unsaturated Acyl Ammonium Catalysis using Silyl Nitronates"

A C=O•••isothiouronium interaction dictates enantiodiscrimination in acylative kinetic resolution of tertiary heterocyclic alcohols (dataset 2)

Cite this