TY - JOUR
T1 - Bismuth(III)-promoted acetylation of thioethers into thioacetates
AU - Jevric, Martyn
AU - Petersen, Anne Ugleholdt
AU - Mansø, Mads
AU - Madsen, Anders Østergaard
AU - Nielsen, Mogens Brøndsted
N1 - DOI: 10.1002/ejoc.201500420
PY - 2015/7/1
Y1 - 2015/7/1
N2 - 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 BiIII 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.
AB - 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 BiIII 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.
U2 - 10.1002/ejoc.201500420
DO - 10.1002/ejoc.201500420
M3 - Journal article
SN - 1434-193X
VL - 2015
SP - 4675
EP - 4688
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
IS - 21
ER -