S-Allyl Thiocarbamates from Allylic Alcohols by in situ [3,3]-Sigmatropic Rearrangement of a Thiocarbonyldiimidazole Adduct

Gaëlle Mingat; Jonathan Clayden

doi:10.1055/s-0032-1316746

Synthesis, Table of Contents

Synthesis 2012; 44(17): 2723-2734
DOI: 10.1055/s-0032-1316746

paper

S-Allyl Thiocarbamates from Allylic Alcohols by in situ [3,3]-Sigmatropic Rearrangement of a Thiocarbonyldiimidazole Adduct

Authors

Gaëlle Mingat

School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK, Fax: +44(161)2754939 Email: clayden@man.ac.uk
Jonathan Clayden*

School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK, Fax: +44(161)2754939 Email: clayden@man.ac.uk

Abstract

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Abstract

Treatment of allylic alcohols with thiocarbonyldiimidazole generates an unstable O-allyl imidazolyl thione ester, which rearranges spontaneously and in high yield to the corresponding S-allyl imidazolyl thiol ester. Displacement of the imidazole by N-alkylanilines in the presence of a nucleophilic catalyst (HOBt or ECHIA) gives S-allyl N-aryl thiocarbamates in excellent yields (up to 97%) over two steps.

Key words

sigmatropic rearrangement - thiocarbamates - alcohols - stereospecificity - sulfur

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References

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