TY - JOUR
T1 - Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates
AU - Matsuo, Yutaka
AU - Yu, Yun
AU - Yang, Xiao Yu
AU - Ueno, Hiroshi
AU - Okada, Hiroshi
AU - Shibuya, Hiromasa
AU - Choi, Yeong Suk
AU - Jin, Yong Wan
PY - 2019/5/17
Y1 - 2019/5/17
N2 - Benzothieno[60]fullerenes were synthesized using fullerenyl cations as key intermediates. The reaction proceeded through a nucleophilic attack of the sulfur atom as a weak nucleophile to the fullerenyl cation electrophile. A monoarylated fullerene, (2-methylthiophenyl)hydro[60]fullerene, C60ArH (Ar = C6H4-SMe-2 and so on; four derivatives) was subjected to deprotonation with KOtBu to form a fullerenyl anion ArC60-, followed by oxidation using I2 to generate a fullerenyl cation ArC60+, leading to intramolecular demethylative cyclization via fullerene cation-S interaction to the product. Electrochemical and computational studies revealed slightly narrower band gap of this compound than usual fullerene derivatives because of the relatively high-lying HOMO of the fused thieno moiety.
AB - Benzothieno[60]fullerenes were synthesized using fullerenyl cations as key intermediates. The reaction proceeded through a nucleophilic attack of the sulfur atom as a weak nucleophile to the fullerenyl cation electrophile. A monoarylated fullerene, (2-methylthiophenyl)hydro[60]fullerene, C60ArH (Ar = C6H4-SMe-2 and so on; four derivatives) was subjected to deprotonation with KOtBu to form a fullerenyl anion ArC60-, followed by oxidation using I2 to generate a fullerenyl cation ArC60+, leading to intramolecular demethylative cyclization via fullerene cation-S interaction to the product. Electrochemical and computational studies revealed slightly narrower band gap of this compound than usual fullerene derivatives because of the relatively high-lying HOMO of the fused thieno moiety.
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U2 - 10.1021/acs.joc.9b00549
DO - 10.1021/acs.joc.9b00549
M3 - Article
C2 - 31006242
AN - SCOPUS:85065766932
VL - 84
SP - 6270
EP - 6277
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 10
ER -