Copper-Catalyzed Aerobic Oxidative Reaction of C₆₀ with Aliphatic Primary Amines and CS₂

Abstract

A novel type of fullerene derivatives, [60]fullerothiazolidinethiones (2), were obtained from the copper-catalyzed aerobic oxidative reaction of C with aliphatic primary amines and CS in 4:1 v/v DMF and o-DCB. The obtained products were fully characterized with the X-ray single-crystal diffraction and spectroscopic methods. Control experiment with maleic anhydride, an analogue to C, also afforded thiazolidinethione product, but via a mechanism different from that of C judging from the structure difference between the two types of thiazolidinethione compounds, demonstrating the unique reactivity of C.

Synthesis of Benzothieno[60]fullerenes through Fullerenyl Cation Intermediates

“…A dimer was predominantly formed through the radical coupling of B when 1 equiv of I 2 was used (Supporting Information). This result indicates that the fullerenyl radical B does not react with the sulfur atom, even though some other C 60 –S compounds are formed through radical reactions . When 5.5 equiv of I 2 was used to oxidize A , the sulfur atom became involved in an unconventional nucleophilic attack to produce a cyclized compound, dihydrobenzothieno[60]­fullerene 2a in 42% isolated yield.…”

“…They are represented by polythiophenes and thiophene-fused aromatic compounds, such as benzodithiophenes and so on, and feature excellent electron-donating and charge carrier transport properties for organic photovoltaics and organic field-effect transistors. , Thiophene-containing fullerene derivatives have been reported widely, with some of them used in application researches . Besides, there are few reports on the modification of fullerene to produce compounds that contain fullerene–sulfur bonds, which are ascribable to the lower nucleophilicity of the sulfur atom toward electrophilic fullerenes compared to carbanions and oxygen atoms. Thus, well-known strategies that use nucleophiles are generally not suitable for the synthesis of C 60 –S compounds.…”

Saturated Five-Membered Thiazolidines and Their Derivatives: From Synthesis to Biological Applications

“…Comparative study of various synthetic protocols [87][88][89][90][91][92][93][94][95][96][97] Fig. 7 Comparative study of various synthetic protocols [98][99][100][101][102] TBAHS in CH 2 Cl 2 at 0 °C, regioisomers of 2-iminothiazolidines were produced in high yields (up to 99%).…”

“…A novel approach for the construction of [60]-fullerothiazolidinethiones from C 60 , aliphatic amines and CS 2 via Cu-catalyzed aerobic oxidative reaction was developed by Wu et al [96] (Scheme 41). The authors applied various catalysts viz.…”

“…Modified from Ref. [96] Scheme 43 Synthesis of thiazolidin-2-imines 51 using metal catalyst amination reaction took place in the C 60 radical anion, O 2 and aminium radical cation to form a C 60 -N bond, followed by Cu-catalyzed aerobic oxidation to produce the C 60 -S bond (Scheme 42).…”