Effects of Solvents on Reaction Products: Synthesis of Endohedral Metallofullerene Oxazoline and Epoxide

Shaoting Yang; Xinyi Zhou; Yajing Hu; Laura Abella; Yang-Rong Yao; Ping Peng; Qianyan Zhang; Antonio Rodríguez-Fortea; Josep M Poblet; Fang-Fang Li

doi:10.1021/acs.joc.2c02779

Effects of Solvents on Reaction Products: Synthesis of Endohedral Metallofullerene Oxazoline and Epoxide

J Org Chem. 2023 Apr 7;88(7):4234-4243. doi: 10.1021/acs.joc.2c02779. Epub 2023 Mar 29.

Authors

Affiliations

¹ State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China.
² Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo 1, 43007 Tarragona, Spain.
³ Department of Materials Science and Engineering, CAS Key Laboratory of Materials for Energy Conversion, Anhui Laboratory of Advanced Photon Science and Technology, University of Science and Technology of China, Hefei 230026, China.
⁴ State Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.

PMID: 36989519
DOI: 10.1021/acs.joc.2c02779

Abstract

Herein, we performed the reactions of M₃N@I_h-C₈₀ (M = Sc and Lu) with the methanol (CH₃OH) solution of TBAOH (note that both CH₃O^- and OH^- are nucleophiles) in benzonitrile (PhCN) and dimethylformamide, respectively. It is found that OH^- ions rather than CH₃O^- ions selectively attacked the fullerene cage to form the M₃N@C₈₀^--O^- intermediate. Although the fullerene cage is initially attacked by OH^- in both PhCN and DMF solvents, the products are quite different. In PhCN, two isomeric Sc₃N@I_h-C₈₀ fullerooxazoline heterocyclic products (1 and 2) were synthesized. Whereas, in DMF, an epoxide of Lu₃N@I_h-C₈₀ (3) was obtained. The preference for fullerooxazoline formation over that of fullerene epoxy in PhCN is well explained by density functional theory calculations. Plausible reaction mechanisms for the formation of metallofullerene oxazoline and epoxide were proposed based on the experimental and theoretical results.