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

Yin-Fu Wu; Shan-Shan Wang; Chun-Rui Yao; Zuo-Chang Chen; Shu-Hui Li; Yang-Rong Yao; Xue-Peng Zhang; Yin Su; Shun-Liu Deng; Qianyan Zhang; Fei Gao; Su-Yuan Xie; Rong-Bin Huang; Lan-Sun Zheng

doi:10.1021/acs.joc.9b01272

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

J Org Chem. 2019 Oct 4;84(19):12259-12267. doi: 10.1021/acs.joc.9b01272. Epub 2019 Aug 6.

Authors

Affiliations

¹ State Key Lab for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry, College of Chemistry and Chemical Engineering , Xiamen University , Xiamen 361005 China.
² College of Chemistry, Chemical Engineering and Environment, Fujian Province Key Laboratory of Modern Analytical Science and Separation Technology , Minnan Normal University , Zhangzhou 363000 China.

PMID: 31315398
DOI: 10.1021/acs.joc.9b01272

Abstract

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.