A hypervalent iodine-promoted intermolecular diamination reactions of C60 with sulfamides or phosphoryl diamides affords two classes of novel C60-fused cyclic sulfamide or phosphoryl diamide derivatives. The reaction between C60 and sulfamides can be effectively controlled to selectively synthesize diamination products or azafulleroids under PhIO/I2 or PhI(OAc)2/I2 conditions, respectively. Moreover, phosphoryl diamides were first used as an amine source in the diamination of alkenes.

An I2-catalyzed hydroxylation of β-dicarbonyl moieties using air as the oxidant under photoirradiation has been developed for the easy preparation of α-hydroxy-β-dicarbonyl compounds. The transformation was completed with only 1 mol % of I2. With α-unsubstituted malonates, the hydroxylated dimerization product was afforded as the predominant product along with a minor product, α,α-dihydroxyl malonate.

The BF3·Et2O-catalyzed formal [3 + 2] reaction of aziridinofullerenes with various carbonyl compounds for the easy preparation of fullerooxazolidines has been developed. Moreover, the reaction of aziridinofullerene with ethyl formate affords the simplest fullerooxazole without substituent.

The hypervalent iodine reagent mediated reaction of C60 with various readily available amines for the easy preparation of iminofullerenes has been developed. The reaction between C60 and sulfonamides can be effectively controlled to selectively synthesize azafulleroids or aziridinofullerenes under PhI(OAc)2/I2 or PhIO/I2/CuCl/lutidine conditions, respectively. For phosphamide and urea, only one isomer is obtained. However, carbamate gives three kinds of products. Interestingly, the reaction of C60 with alkylamines allows the effective synthesis of aziridinofullerenes and regioselective cis-1-bisaziridinofullerenes.

The Cu(OAc)2-promoted reaction of C60 with easily available primary amines allows the concise preparation of aziridinofullerenes. Both alkyl and aryl amines are suitable in this reaction. Moreover, the Cu(OAc)2-promoted reaction of C60 with diamines affords C60-fused cyclic 1,2-diaminated fullerenes.

The Lewis base-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with various ureas allows the easy preparation of fulleroimidazolidinones with a high tolerance for functional groups. Alkyl-substituted ureas show better reactivity than aryl-substituted ureas.

BF3·Et2O-catalyzed double nucleophilic substitution reaction of N-tosylaziridinofullerene with sulfamides has been exploited for the easy preparation of cyclic sulfamide-fused fullerene derivatives. Moreover, the Lewis base catalyzed double amination of N-tosylaziridinofullerene, with amidines as the diamine source, is demonstrated for the first time. The present methods provide new routes to cyclic 1,2-diaminated [60]fullerenes.

Cu(OAc) 2-Promoted Reaction of [60]Fullerene with Primary Amines or Diamines. -The title reaction allows the concise preparation of aziridinofullerenes. Both alkyl and aryl amines are suitable in this reaction. Moreover, the Cu(OAc) 2-promoted reaction of C60 with diamines affords C60-fused cyclic 1,2-diaminated fullerenes. -(LU, X.-W.; XING, M.-L.; MIAO, C.-B.; LI, J.-X.; SUN*, X.-Q.; YANG, H.-T.; Org. Biomol. Chem. 13 (2015) 31, 8405-8410, http://dx.