Evaluating aryl esters as bench-stable C(1)-ammonium enolate precursors in catalytic, enantioselective Michael addition-lactonisations

Claire M. Young; James E. Taylor; Andrew D. Smith

doi:10.1039/C9OB00703B

Evaluating aryl esters as bench-stable C(1)-ammonium enolate precursors in catalytic, enantioselective Michael addition-lactonisations

Claire M. Young, James E. Taylor, Andrew D. Smith

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

Abstract

An evaluation of a range of aryl, alkyl and vinyl esters as prospective C(1)-ammonium enolate precursors in enantioselective Michael addition-lactonisation processes with (E)-trifluoromethylenones using isothiourea catalysis is reported. Electron deficient aryl esters are required for reactivity, with 2,4,6-trichlorophenyl esters providing optimal product yields. Catalyst screening showed that tetramisole was the most effective isothiourea catalyst, giving the desired dihydropyranone product in excellent yield and stereoselectivity (up to 90:10 dr and 98:2 er). The scope and limitations of this process have been evaluated, with a range of diester products being generated after ring-opening with MeOH to give stereodefined dihydropyranones with excellent stereocontrol (10 examples, typically ~90:10 dr and >95:5 er).

Original language	English
Pages (from-to)	4747-4752
Journal	Organic & Biomolecular Chemistry
Volume	17
Issue number	19
Early online date	11 Apr 2019
DOIs	https://doi.org/10.1039/C9OB00703B
Publication status	Published - 21 May 2019

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10.1039/C9OB00703B

Young_2019_OBC_Arylesters_AAM
Copyright © 2019 The Author(s). This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version 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/10.1039/C9OB00703B
Accepted author manuscript, 470 KB

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
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

Data underpinning "Evaluating Aryl Esters as Bench-Stable C(1)-Ammonium Enolate Precursors in Catalytic, Enantioselective Michael Addition-Lactonisations"
Young, C. M. (Owner), Taylor, J. E. (Creator) & Smith, A. D. (Creator), University of St Andrews, 15 Apr 2019
DOI: 10.17630/cb133261-b58e-4d72-b380-c877c993dc5d
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@article{e85c986f599c4da7b2c9222cac72c267,

title = "Evaluating aryl esters as bench-stable C(1)-ammonium enolate precursors in catalytic, enantioselective Michael addition-lactonisations",

abstract = "An evaluation of a range of aryl, alkyl and vinyl esters as prospective C(1)-ammonium enolate precursors in enantioselective Michael addition-lactonisation processes with (E)-trifluoromethylenones using isothiourea catalysis is reported. Electron deficient aryl esters are required for reactivity, with 2,4,6-trichlorophenyl esters providing optimal product yields. Catalyst screening showed that tetramisole was the most effective isothiourea catalyst, giving the desired dihydropyranone product in excellent yield and stereoselectivity (up to 90:10 dr and 98:2 er). The scope and limitations of this process have been evaluated, with a range of diester products being generated after ring-opening with MeOH to give stereodefined dihydropyranones with excellent stereocontrol (10 examples, typically ~90:10 dr and >95:5 er).",

author = "Young, {Claire M.} and Taylor, {James E.} and Smith, {Andrew D.}",

note = "We thank the European Research Council under the European Union{\textquoteright}s Seventh Framework Programme (FP7/2007-2013) ERC Grant Agreement no. 279850 (CMY, JET). ADS thanks the Royal Society for a Wolfson Merit Award. We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University. The data underpinning this research can be found at DOI: https://doi.org/10.17630/cb133261-b58e-4d72-b380-c877c993dc5d",

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T1 - Evaluating aryl esters as bench-stable C(1)-ammonium enolate precursors in catalytic, enantioselective Michael addition-lactonisations

AU - Young, Claire M.

AU - Taylor, James E.

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 no. 279850 (CMY, JET). ADS thanks the Royal Society for a Wolfson Merit Award. We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University. The data underpinning this research can be found at DOI: https://doi.org/10.17630/cb133261-b58e-4d72-b380-c877c993dc5d

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Y1 - 2019/5/21

N2 - An evaluation of a range of aryl, alkyl and vinyl esters as prospective C(1)-ammonium enolate precursors in enantioselective Michael addition-lactonisation processes with (E)-trifluoromethylenones using isothiourea catalysis is reported. Electron deficient aryl esters are required for reactivity, with 2,4,6-trichlorophenyl esters providing optimal product yields. Catalyst screening showed that tetramisole was the most effective isothiourea catalyst, giving the desired dihydropyranone product in excellent yield and stereoselectivity (up to 90:10 dr and 98:2 er). The scope and limitations of this process have been evaluated, with a range of diester products being generated after ring-opening with MeOH to give stereodefined dihydropyranones with excellent stereocontrol (10 examples, typically ~90:10 dr and >95:5 er).

AB - An evaluation of a range of aryl, alkyl and vinyl esters as prospective C(1)-ammonium enolate precursors in enantioselective Michael addition-lactonisation processes with (E)-trifluoromethylenones using isothiourea catalysis is reported. Electron deficient aryl esters are required for reactivity, with 2,4,6-trichlorophenyl esters providing optimal product yields. Catalyst screening showed that tetramisole was the most effective isothiourea catalyst, giving the desired dihydropyranone product in excellent yield and stereoselectivity (up to 90:10 dr and 98:2 er). The scope and limitations of this process have been evaluated, with a range of diester products being generated after ring-opening with MeOH to give stereodefined dihydropyranones with excellent stereocontrol (10 examples, typically ~90:10 dr and >95:5 er).

U2 - 10.1039/C9OB00703B

DO - 10.1039/C9OB00703B

M3 - Article

SN - 1477-0520

VL - 17

SP - 4747

EP - 4752

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 19

ER -

Evaluating aryl esters as bench-stable C(1)-ammonium enolate precursors in catalytic, enantioselective Michael addition-lactonisations

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Projects

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

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

Datasets

Data underpinning "Evaluating Aryl Esters as Bench-Stable C(1)-Ammonium Enolate Precursors in Catalytic, Enantioselective Michael Addition-Lactonisations"

Cite this