Synthesis 2012; 44(17): 2723-2734
DOI: 10.1055/s-0032-1316746
paper
© Georg Thieme Verlag Stuttgart · New York

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

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
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Publikationsverlauf

Received: 18. April 2012

Accepted after revision: 22. Juni 2012

Publikationsdatum:
30. Juli 2012 (online)


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.

Supporting Information