BF₃·Et₂O- or DMAP-Catalyzed Double Nucleophilic Substitution Reaction of Aziridinofullerenes with Sulfamides or Amidines

Abstract

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.

Lewis Base-Catalyzed Reaction of Aziridinofullerene with Ureas for the Preparation of Fulleroimidazolidinones

“…We also explored the reaction of Ntosylaziridinofullerene with sulfamides or amidines for the easy preparation of C 60 -fused cyclic diaminated fullerenes. 5 C 60 has been the most striking electron-acceptor because of its high electron affinity and low reorganization energies for electron transfer. 6 The design and synthesis of new fullerene derivatives with improved electron affinity is a very appealing task in the search of their applications in materials science.…”

“…Recently we have been interested in the development of new routes to cyclic diaminated [60]fullerenes starting from Ntosylaziridinofullerene. 5 The reaction conditions were found to vary greatly with different diamine sources. The reaction of sulfamides with N-tosylaziridinofullerene could be accomplished well using BF reaction of amidines with N-tosylaziridinofullerene, Lewis acids showed no catalytic activity.…”

“…Later, the formal [3 + 2] reactions of N -tosylaziridinofullerene with CO 2 , isocyanates, and carbonyls were developed. We also explored the reaction of N -tosylaziridinofullerene with sulfamides or amidines for the easy preparation of C 60 -fused cyclic diaminated fullerenes …”

“…Recently we have been interested in the development of new routes to cyclic diaminated [60]fullerenes starting from N -tosylaziridinofullerene . The reaction conditions were found to vary greatly with different diamine sources.…”

Synthesis of Aziridinofullerene-Porphyrin Mediated by Triethyl Phosphite: Physicochemical and Electrochemical Properties

“…High reactivity, explosiveness and toxicity of azide forced researchers to find new strategies for aziridinofullerene synthesis. Aziridination of fullerene using copper catalyzed with TsN=IPh, pyridine‐copper complex catalyzed N‐Tosyloxycarbamates, aziridination of fullerene with chloramines‐T, sulfilimine, iminoiodane, iminophenyliodine, and N,N‐dihalosulfonamides have been reported. Apart from the preparation of pyrrolidinofullerene‐porphyrin, all the aziridination methods followed two or more reaction steps.…”