Hetero-diels-alder reaction of fullerene: Synthesis of thiochroman-fused C60 with o-thioquinone methide and oxidation to its S-oxides

One-pot synthesis of new thio-derivatives of C60with the unexpected formation of a thiazolidine-fulleropyrrolidine

“…To investigate further the effect of the aldehyde on the formation of the fulleropyrrolidine, similar reactions of C 60 with different aldehydes (9,11) were also studied, resulting in the synthesis of other two new thio-derivatives of C 60 , 10 and 12. While 10 has an analogous structure to 6, 12 is one of the few compounds reported that integrates a thiophene ring into a fulleropyrrolidine.…”

“…4 Using versatile sulfur-containing reagents, a number of thio-derivatives of fullerenes have been synthesized. [4][5][6][7][8][9][10][11][12] While sulfones 5 and sultines 6 were used as the main sulfurcontaining reagents for the synthesis of C 60 -chlorin dyads 7 and C 60 -porphyrin hybrids, 5 other sulfur sources (such as sulfonium ylides, 8 o-thioquinone methides, 9 a,b-unsaturated thiocarbonyl compounds, 10 thiocarbonyl ylides, 11 and the heterocyclic masked 1,3-dipole 5-imino-1,2,4-thiadiazolidine-3-one 12 ) have also been applied for the synthesis of thioderivatives of fullerenes. Despite the versatility of these syntheses, it is noted that in general most of them are rather complicated.…”

Four‐Membered Heterocycles: Structure and Reactivity

“…In the absence of dienophile, a dimer of methylenecyclohexadienethione is formed. Reaction of this compound with C 60 [352], imines and diazenes [353] has also been reported. …”

Cycloadditions

“…A few examples of hetero-Diels-Alder adducts have been reported [75][76][77][78][79][80][81]. A thiochroman-fused fullerene adduct was synthesized by the reaction of o-thioquinone with C 60 in o-dichlorobenzene at 180 °C [77].…”