Bismuth(III)-promoted acetylation of thio­ethers into thioacetates

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 -