Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates

Yutaka Matsuo; Yun Yu; Xiao Yu Yang; Hiroshi Ueno; Hiroshi Okada; Hiromasa Shibuya; Yeong Suk Choi; Yong Wan Jin

doi:10.1021/acs.joc.9b00549

Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates

Yutaka Matsuo, Yun Yu, Xiao Yu Yang, Hiroshi Ueno, Hiroshi Okada, Hiromasa Shibuya, Yeong Suk Choi, Yong Wan Jin

Research output: Contribution to journal › Article › peer-review

6 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	6270-6277
Number of pages	8
Journal	Journal of Organic Chemistry
Volume	84
Issue number	10
DOIs	https://doi.org/10.1021/acs.joc.9b00549
Publication status	Published - 2019 May 17
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

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title = "Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates",

abstract = "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.",

author = "Yutaka Matsuo and Yun Yu and Yang, {Xiao Yu} and Hiroshi Ueno and Hiroshi Okada and Hiromasa Shibuya and Choi, {Yeong Suk} and Jin, {Yong Wan}",

note = "Funding Information: Funding from the University of Science and Technology of China is gratefully acknowledged. This work was also supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI grant nos JP15H05760, JP16H04187, JP17K19116, and 17 K04970) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. The computational work was performed at Research Center for Computational Science, Okazaki, Japan. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = may,

day = "17",

doi = "10.1021/acs.joc.9b00549",

language = "English",

volume = "84",

pages = "6270--6277",

journal = "Journal of Organic Chemistry",

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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

N1 - Funding Information: Funding from the University of Science and Technology of China is gratefully acknowledged. This work was also supported by Grants-in-Aid for Scientific Research (JSPS KAKENHI grant nos JP15H05760, JP16H04187, JP17K19116, and 17 K04970) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan. The computational work was performed at Research Center for Computational Science, Okazaki, Japan. Publisher Copyright: © 2019 American Chemical Society.

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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Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates

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