2 + 1] Cycloaddition reactions of fullerene C60 based on diazo compounds.

Yuliya N Biglova

doi:10.3762/bjoc.17.55

Abstract

The most common variant of fullerene core functionalization is the [2 + 1] cycloaddition process. Of these, reactions leading to methanofullerenes are the most promising. They are synthesized in two main reactions: nucleophilic cyclopropanation according to the Bingel method and thermal addition of diazo compounds. This present review summarizes the material on the synthesis of monofunctionalized methanofullerenes – analogues of [60]PCBM – based on various diazo compounds. The main cyclopropanating agents for the synthesis of monosubstituted methanofullerenes, the optimal conditions and the mechanism of the [2 + 1] cycloaddition, as well as the practical application of the target products are analyzed.

Highlights

Taking into consideration that all life on Earth is of organic origin. with carbon as its basic element (20% by weight of every living organism, and the fourth most abundant element in the universe), the discovery in 1985 of its new allotropic modification, fullerene, has resulted in an avalanche-like expansion of studies in this area [1]
All of them were synthesized under conditions similar to those indicated in Scheme 24 (Figure 8) [112]
Unusual spiromethanofullerenes were presented in reference [157], where the synthesis of N,N-(tetrachlorophthaloyl)dehydroabietylamine derivatives 198–201 from dehydroabietylamine substituted by fullerene in ring B was reported (Scheme 36)

Summary

Introduction

Taking into consideration that all life on Earth is of organic origin. with carbon as its basic element (20% by weight of every living organism, and the fourth most abundant element in the universe), the discovery in 1985 of its new allotropic modification, fullerene, has resulted in an avalanche-like expansion of studies in this area [1]. C60 adducts were doped with tetrakis(dimethylamino)ethylene (TDAE) and cobaltocene (Cp2Co) in order to create charge-transfer complexes with the purpose of searching for efficient magnetic materials based on fullerenes It can be seen in Scheme 16 that methanofullerene 52 was obtained from the initial, para-substituted, ethyl diazo(4-nitrophenyl)acetate in 32% yield [100]. In the development of new organometallic C60 compounds that can be used as homogeneous catalysts, new blocks 61 and 62, cross-conjugated through cyclopropane, were synthesized (Scheme 19) [104] Attaching such an electron-enriched metal-containing system to C60 can result in push–pull blocks with new electronic and photochemical properties, as demonstrated by complexes 63, [103], and [104] in Scheme 13: Serial synthesis of monophenylmethanofullerenes. All of them were synthesized under conditions similar to those indicated in Scheme 24 (Figure 8) [112]

Synthesis of methanofullerenes with tosylhydrazone

Conclusion

Findings

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