Isothiourea-catalysed acylative kinetic resolution of aryl-alkenyl (sp2 vs. sp2) substituted secondary alcohols

Stefania F. Musolino; O. Stephen Ojo; Nicholas J. Westwood; James E. Taylor; Andrew D. Smith

doi:10.1002/chem.201604788

Isothiourea-catalysed acylative kinetic resolution of aryl-alkenyl (sp² vs. sp²) substituted secondary alcohols

Stefania F. Musolino, O. Stephen Ojo, Nicholas J. Westwood, James E. Taylor, Andrew D. Smith

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

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Abstract

The non-enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp² vs. sp²) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol %) and isobutyric anhydride. The kinetic resolution of a wide range of aryl–alkenyl substituted alcohols has been evaluated, with either electron-rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S=2–1980). The use of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl–vinyl (sp² vs. sp²) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.

Original language	English
Pages (from-to)	18916-18922
Number of pages	8
Journal	Chemistry - A European Journal
Volume	22
Issue number	52
Early online date	30 Nov 2016
DOIs	https://doi.org/10.1002/chem.201604788
Publication status	Published - 23 Dec 2016

Keywords

Kinetic resolution
Acylation
Organocatalysis
Isothiourea
Renewable resources

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/chem.201604788Licence: CC BY

Smith_2016_CEJ_SubstitutedSecondaryAlcohols_CC
© 2016 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, 894 KBLicence: CC BY

Catalytic Activation: Catalytic Activation of Carboxylic Acids and Alcohols
Taylor, J. E. (PI)
The Leverhulme Trust
1/05/15 → 30/04/18
Project: Fellowship
CRITICAT CDT: Critical Resource Catalysis - CRITICAT
Smith, A. D. (PI), Nolan, S. P. (CoI) & Westwood, N. J. (CoI)
EPSRC
1/05/14 → 31/10/22
Project: Standard
Clean catalysis for sustainable develop: Clean catalysis for sustainable development
Kamer, P. C. J. (PI)
EPSRC
1/11/12 → 31/10/17
Project: Standard

Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl-Alkenyl (sp2 vs sp2) Substituted Secondary Alcohols
Smith, A. D. (Creator), Musolino, S. F. (Contributor), Ojo, O. S. (Contributor), Westwood, N. J. (Owner) & Taylor, J. E. (Owner), University of St Andrews, 2016
DOI: 10.17630/5b5c7f5a-7329-40b7-aaed-907c94dff692
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Cite this

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title = "Isothiourea-catalysed acylative kinetic resolution of aryl-alkenyl (sp2 vs. sp2) substituted secondary alcohols",

abstract = "The non-enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp2 vs. sp2) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol %) and isobutyric anhydride. The kinetic resolution of a wide range of aryl–alkenyl substituted alcohols has been evaluated, with either electron-rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S=2–1980). The use of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl–vinyl (sp2 vs. sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.",

keywords = "Kinetic resolution, Acylation, Organocatalysis, Isothiourea, Renewable resources ",

author = "Musolino, {Stefania F.} and Ojo, {O. Stephen} and Westwood, {Nicholas J.} and Taylor, {James E.} and Smith, {Andrew D.}",

note = "We would like to thank the Engineering and Physical Sciences Research Council and CRITICAT Centre for Doctoral Training [Ph.D. studentship to S.F.M.; Grant code: EP/L016419/1 and EP/J018139/1] and The Leverhulme Trust [Early Career Fellowship to J.E.T.; ECF-2014-005] for financial support. A.D.S. thanks the Royal Society for a Wolfson Merit Award.",

year = "2016",

month = dec,

day = "23",

doi = "10.1002/chem.201604788",

language = "English",

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pages = "18916--18922",

journal = "Chemistry - A European Journal",

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T1 - Isothiourea-catalysed acylative kinetic resolution of aryl-alkenyl (sp2 vs. sp2) substituted secondary alcohols

AU - Musolino, Stefania F.

AU - Ojo, O. Stephen

AU - Westwood, Nicholas J.

AU - Taylor, James E.

AU - Smith, Andrew D.

N1 - We would like to thank the Engineering and Physical Sciences Research Council and CRITICAT Centre for Doctoral Training [Ph.D. studentship to S.F.M.; Grant code: EP/L016419/1 and EP/J018139/1] and The Leverhulme Trust [Early Career Fellowship to J.E.T.; ECF-2014-005] for financial support. A.D.S. thanks the Royal Society for a Wolfson Merit Award.

PY - 2016/12/23

Y1 - 2016/12/23

N2 - The non-enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp2 vs. sp2) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol %) and isobutyric anhydride. The kinetic resolution of a wide range of aryl–alkenyl substituted alcohols has been evaluated, with either electron-rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S=2–1980). The use of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl–vinyl (sp2 vs. sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.

AB - The non-enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp2 vs. sp2) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol %) and isobutyric anhydride. The kinetic resolution of a wide range of aryl–alkenyl substituted alcohols has been evaluated, with either electron-rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S=2–1980). The use of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl–vinyl (sp2 vs. sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.

KW - Kinetic resolution

KW - Acylation

KW - Organocatalysis

KW - Isothiourea

KW - Renewable resources

U2 - 10.1002/chem.201604788

DO - 10.1002/chem.201604788

M3 - Article

SN - 0947-6539

VL - 22

SP - 18916

EP - 18922

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 52

ER -

Isothiourea-catalysed acylative kinetic resolution of aryl-alkenyl (sp2 vs. sp2) substituted secondary alcohols

Abstract

Keywords

UN SDGs

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Projects

Catalytic Activation: Catalytic Activation of Carboxylic Acids and Alcohols

CRITICAT CDT: Critical Resource Catalysis - CRITICAT

Clean catalysis for sustainable develop: Clean catalysis for sustainable development

Datasets

Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl-Alkenyl (sp2 vs sp2) Substituted Secondary Alcohols

Cite this

Isothiourea-catalysed acylative kinetic resolution of aryl-alkenyl (sp² vs. sp²) substituted secondary alcohols