Stereo- and chemodivergent NHC-promoted functionalisation of arylalkylketenes with chloral

James Douglas; Gwydion Churchill; Alexandra Martha Zoya Slawin; David J. Fox; Andrew David Smith

doi:10.1002/chem.201503308

Stereo- and chemodivergent NHC-promoted functionalisation of arylalkylketenes with chloral

James Douglas, Gwydion Churchill, Alexandra Martha Zoya Slawin, David J. Fox, Andrew David Smith

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

25 Citations (Scopus)

7 Downloads (Pure)

Abstract

Stereo- and chemodivergent enantioselective reaction pathways are observed upon treatment of alkylarylketenes and trichloroacetaldehyde (chloral) with N-heterocyclic carbenes, giving selectively either β-lactones (up to 88:12 dr, up to 94 % ee) or α-chloroesters (up to 94 % ee). Either 2-arylsubstitution or an α-branched iPr alkyl substituent within the ketene favours the chlorination pathway, allowing chloral to be used as an electrophilic chlorinating reagent in asymmetric catalysis.

Original language	English
Pages (from-to)	16354–16358
Journal	Chemistry - A European Journal
Volume	21
Issue number	46
Early online date	25 Sept 2015
DOIs	https://doi.org/10.1002/chem.201503308
Publication status	Published - 9 Nov 2015

Keywords

Asymmetric catalysis
Chlorination reactions
Ketenes
Lactones
Stereodivergent reactions

Access to Document

10.1002/chem.201503308Licence: CC BY

Smith_2015_CEUJ_Stereo_CC
© 2015 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, 627 KB

Cite this

@article{2e100f6fa23d411facc12dddfd28836b,

title = "Stereo- and chemodivergent NHC-promoted functionalisation of arylalkylketenes with chloral",

abstract = "Stereo- and chemodivergent enantioselective reaction pathways are observed upon treatment of alkylarylketenes and trichloroacetaldehyde (chloral) with N-heterocyclic carbenes, giving selectively either β-lactones (up to 88:12 dr, up to 94 % ee) or α-chloroesters (up to 94 % ee). Either 2-arylsubstitution or an α-branched iPr alkyl substituent within the ketene favours the chlorination pathway, allowing chloral to be used as an electrophilic chlorinating reagent in asymmetric catalysis.",

keywords = "Asymmetric catalysis, Chlorination reactions, Ketenes, Lactones, Stereodivergent reactions",

author = "James Douglas and Gwydion Churchill and Slawin, {Alexandra Martha Zoya} and Fox, {David J.} and Smith, {Andrew David}",

note = "Funding: UK Engineering and Physical Sciences Research Council EP/G501742/1 ",

year = "2015",

month = nov,

day = "9",

doi = "10.1002/chem.201503308",

language = "English",

volume = "21",

pages = "16354–16358",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley & Sons, Ltd",

number = "46",

}

TY - JOUR

T1 - Stereo- and chemodivergent NHC-promoted functionalisation of arylalkylketenes with chloral

AU - Douglas, James

AU - Churchill, Gwydion

AU - Slawin, Alexandra Martha Zoya

AU - Fox, David J.

AU - Smith, Andrew David

N1 - Funding: UK Engineering and Physical Sciences Research Council EP/G501742/1

PY - 2015/11/9

Y1 - 2015/11/9

N2 - Stereo- and chemodivergent enantioselective reaction pathways are observed upon treatment of alkylarylketenes and trichloroacetaldehyde (chloral) with N-heterocyclic carbenes, giving selectively either β-lactones (up to 88:12 dr, up to 94 % ee) or α-chloroesters (up to 94 % ee). Either 2-arylsubstitution or an α-branched iPr alkyl substituent within the ketene favours the chlorination pathway, allowing chloral to be used as an electrophilic chlorinating reagent in asymmetric catalysis.

AB - Stereo- and chemodivergent enantioselective reaction pathways are observed upon treatment of alkylarylketenes and trichloroacetaldehyde (chloral) with N-heterocyclic carbenes, giving selectively either β-lactones (up to 88:12 dr, up to 94 % ee) or α-chloroesters (up to 94 % ee). Either 2-arylsubstitution or an α-branched iPr alkyl substituent within the ketene favours the chlorination pathway, allowing chloral to be used as an electrophilic chlorinating reagent in asymmetric catalysis.

KW - Asymmetric catalysis

KW - Chlorination reactions

KW - Ketenes

KW - Lactones

KW - Stereodivergent reactions

UR - http://onlinelibrary.wiley.com/doi/10.1002/chem.201503308/suppinfo

U2 - 10.1002/chem.201503308

DO - 10.1002/chem.201503308

M3 - Article

SN - 0947-6539

VL - 21

SP - 16354

EP - 16358

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 46

ER -

Stereo- and chemodivergent NHC-promoted functionalisation of arylalkylketenes with chloral

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Structuring the Future: Structuring the Future - Underpinning world-leading science in EaStCHEM through cutting edge characterisation

Robotically Automated Crystallography: St Andrews Robotically Automated Crystallography