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Bismuth(III)‐Promoted Acetylation of Thioethers into Thioacetates
Author(s) -
Jevric Martyn,
Petersen Anne Ugleholdt,
Mansø Mads,
Madsen Anders Østergaard,
Nielsen Mogens Brøndsted
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500420
Subject(s) - chemistry , thioether , combinatorial chemistry , molecule , thio , azide , halide , bismuth , hydrolysis , environmentally friendly , redox , organic chemistry , functional group , polymer chemistry , polymer , ecology , biology
The thioacetate group is extensively employed as an anchoring group for attachment of molecules onto gold surfaces or between electrodes in molecular electronics. On account of its ready hydrolysis, it is often incorporated in the last step of a synthetic sequence from the corresponding tert ‐butyl thioether. Here we present a particularly convenient method for this conversion using AcCl in combination with Bi(OTf) 3 , which is known as an environmentally friendly salt. A large variety of redox‐active and photoactive substrates with tert ‐butyl thioether end‐cap(s) was prepared, including molecules incorporating dithiafulvene, dicyanoethylene, dihydroazulene, fulleropyrrolidine, and triazole units, and successfully subjected to a Bi III promoted conversion into products with thioacetate end‐cap(s). The azide group could also withstand these conditions, which allowed us to prepare S ‐(4‐azidophenyl) ethanethioate that presents a convenient building block for subsequent CuAAC reactions.