Hypervalent Iodine Reagent Mediated Reaction of [60]Fullerene with Amines

Abstract

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.

Hypervalent Iodine Reagent Mediated Diamination of [60]Fullerene with Sulfamides or Phosphoryl Diamides

“…On the basis of these results and our previous work on the hypervalent iodine-mediated reaction of C 60 with amines, a radical reaction mechanism for the selective transformation is proposed in Scheme . N -Iodo intermediate 5 was generated under both reaction conditions.…”

“…Recently, cobalt-catalyzed radical hydroalkylation or cycloaddition of C 60 with active alkyl bromides or dibromides was demonstrated. , In contrast to the most investigated addition of C-centered radicals to fullerenes, the addition of N-centered radicals to fullerenes was rather rare. Only a few reactions of C 60 with nitriles, amidines, amides, and carbamates based on N-centered radicals were exploited. , Recently, we developed a hypervalent iodine reagent/I 2 system-mediated or CuI-catalyzed N-centered radical reactions of C 60 with amines/amides/amidines. , …”

“…However, this approach was limited to an intramolecular addition fashion, and the use of phosphoryl diamides as amine source has never been investigated. The new methods for the preparation of fullerooxazoles and iminofullerenes explored by us and Minakata’s group , disclosed the nitrogen radicals were easy to generate through N–I bond cleavage from the N , N -diiodo intermediate and took place radical reaction with C 60 . Inspired by these results, we could envision that treatment of sulfamides or phosphoryl diamides with hypervalent iodine reagents/I 2 would generate the N , N ′-diiodo intermediate, which might be captured by C 60 in a radical pathway to generate novel C 60 -fused cyclic diamine derivatives (Scheme ).…”

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…This system is also useful for generating nitrogen radicals. ,,− For example, the nitrogen radical species, generated from the N -alkylsaccharins 287 and DIB in the presence of iodine under irradiation with a tungsten lamp, are key intermediates in the intramolecular coupling reaction to give arenesulfonamides 288 (Scheme ). …”

Recent Advances in Iodosobenzene‐Mediated Construction of Heterocyclic Scaffolds: Transition‐Metal‐Free Approaches and Scope

“…Synthetic organic chemists are involved in a continuous effort to reveal the excellent Lewis acidic oxidizing characteristics of these reagents from the last decade of the 20 th century to recent years. These reagents led to rapid development in the modern field of C–C/C–X (X = O, N, halogens) coupling and cyclization reactions . Some chiral hypervalent iodine reagents were also in the limelight for asymmetric synthesis .…”