Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl–Alkenyl (sp2vs. 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 (sp²vs. sp²) Substituted Secondary Alcohols

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

Department of Chemistry

University of St Andrews

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

33 Citations (SciVal)

Abstract

The non-enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp²vs. 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 (sp²vs. 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	7
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 - 21 Dec 2016

UN SDGs

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

SDG 7 Affordable and Clean Energy

Keywords

acylation
isothiourea
kinetic resolution
organocatalysis
renewable resources

ASJC Scopus subject areas

General Chemistry

Access to Document

10.1002/chem.201604788Licence: CC BY

Cite this

@article{9877f7648df44afea29cf34f651a377f,

title = "Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl{\textendash}Alkenyl (sp2vs. sp2) Substituted Secondary Alcohols",

abstract = "The non-enzymatic acylative kinetic resolution of challenging aryl{\textendash}alkenyl (sp2vs. 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{\textendash}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{\textendash}1980). The use of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl{\textendash}vinyl (sp2vs. sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.",

keywords = "acylation, isothiourea, kinetic resolution, organocatalysis, renewable resources",

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

year = "2016",

month = dec,

day = "21",

doi = "10.1002/chem.201604788",

language = "English",

volume = "22",

pages = "18916--18922",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "John Wiley and Sons Inc.",

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TY - JOUR

T1 - Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl–Alkenyl (sp2vs. sp2) Substituted Secondary Alcohols

AU - Musolino, Stefania F.

AU - Ojo, O. Stephen

AU - Westwood, Nicholas J.

AU - Taylor, James E.

AU - Smith, Andrew D.

PY - 2016/12/21

Y1 - 2016/12/21

N2 - The non-enzymatic acylative kinetic resolution of challenging aryl–alkenyl (sp2vs. 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 (sp2vs. 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 (sp2vs. 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 (sp2vs. sp2) substituted secondary alcohol is demonstrated, giving access to >1 g of each of the product enantiomers both in 99:1 e.r.

KW - acylation

KW - isothiourea

KW - kinetic resolution

KW - organocatalysis

KW - renewable resources

UR - https://www.scopus.com/pages/publications/85006791371

U2 - 10.1002/chem.201604788

DO - 10.1002/chem.201604788

M3 - Article

AN - SCOPUS:85006791371

SN - 0947-6539

VL - 22

SP - 18916

EP - 18922

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 52

ER -