General One-step Synthesis of Symmetrical or Unsymmetrical 1,4-Di(organo)fullerenes from Organo(hydro)fullerenes through Direct Oxidative Arylation

• Published in: Journal of organic chemistry 2019-10, Vol.84 (19), p.12259-12267
• Main Authors: Wu, Yin-Fu, Wang, Shan-Shan, Yao, Chun-Rui, Chen, Zuo-Chang, Li, Shu-Hui, Yao, Yang-Rong, Zhang, Xue-Peng, Su, Yin, Deng, Shun-Liu, Zhang, Qianyan, Gao, Fei, Xie, Su-Yuan, Huang, Rong-Bin, Zheng, Lan-Sun
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.9b01272

A general one-step synthesis of symmetrical or unsymmetrical 1,4-di­(organo)­fullerenes from organo­(hydro)­fullerenes (RC60H) is realized by direct oxidative arylation. The new combination of catalytic trifluoromethanesulfonic acid (TfOH) and stoichiometric o-chloranil is the first to be used to directly generate an R-C60 + intermediate from common RC60H. Unexpectedly, the in situ generated R-C60 + intermediate is shown to be quite stable in whole 13C NMR spectroscopy characterization in the absence of cation quenching reagents. Because the direct oxidation of common RC60H to form the corresponding R-C60 + has never been realized, the present combination of TfOH and o-chloranil solves the challenges associated with the formation of stable RC60 + cations from common RC60H without any coordination of an R group.