Arslan R. Akhmetov

Catalytic [2+1]-cycloaddition of ethyl diazoacetate to fullerene [60]

Cyclopropanation of C60-fullerene was performed with ethyl diazoacetate in the presence of Pd(PPh3)4 catalyst. A probable reaction mechanism is suggested.

Synthesis of functionally substituted methanofullerenes and study of their tribological properties

Possibility of synthesizing functionally substituted methanofullerenes by cycloaddition of diazo derivatives of methionine and threonine to C60 fullerene in the presence of a three-component catalytic system Pd(acac)2-PPh3-Et3Al was examined. Tribological characteristics of the resulting compound as an additive to an industrial oil were studied.

Synthesis and 13C NMR features of N-substituted aziridino[60]fullerenes

An effective cycloaddition of organic azides to fullerene C60 in the presence stoichiometric amounts of Cu(OTf)2 to form individual aziridino[60]fullerenes was developed. Considering the 13C NMR data, it was ascertained that among the synthesized aziridinofullerenes only the compound with the adamantane substituent possessed the local C2v symmetry of the fullerene core. In the 13C NMR spectra of the other compounds, 11 resonances were unexpectedly observed for the fullerene carbon atoms instead of probable 16 signals. The 13C NMR chemical shifts were computed with the high level GIAO-PBE/3ζ technique and the possible reasons of the signal overlap in the 13C NMR spectra were discussed.

Selective cycloaddition of aryl azides to fullerene C60 in the presence of Cu(OTf)2

Cycloaddition of aryl azides to fullerene C60 in the presence of a stoichiometric amount of copper(II) trifluoromethanesulfonate selectively afforded the corresponding aziridinofullerenes whose structure was reliably proved by 1H and 13C NMR, MALDI TOF mass spectrometry, and IR spectroscopy.

Synthesis and Properties of Energy-Rich Methanofullerenes Containing Norbornadiene and Quadricyclane Moieties

The energy-rich methanofullerenes were synthesized for the first time by the reaction of fullerene C60 with mono- and bisquadricyclane esters of malonic acid. The C-C bond cleavage in the quadricyclane moieties of new hybrid molecules takes place in the presence of catalytic amounts of Cu, Pd, and Pt salts or complexes or SiO2 and is accompanied by heat evolution.

Synthesis and photochromic properties of hybrid molecules based on fullerene C 60 and 3,3′-(cyclopent-1-ene-1,2-diyl)bis(5-chloro-2-methylthiophene)

A series of C60 adducts with azides derived from 3,3′-(cyclopent-1-ene-1,2-diyl)bis(5-chloro-2-methylthiophene) have been synthesized for the first time, and their photochromic properties have been studied. The effects of the structure of the spacer connecting the fullerene and dihetarylethene moieties and electronic structure of the fullerene skeleton on the efficiency of photoinduced transformations of the new hybrid molecules have been estimated.

Catalytic [3+2]-cycloaddition of dialkyl, diallyl, and dibenzyl sulfides to fullerene C60

Increased interest in heteroring-fused fullerenes originates from their wide medical and technical applications [1, 2]. A general procedure for the synthesis of fullerenes with fused N,O,S-containing heterorings is based on 1,3-dipolar cycloaddition of ylides generated in situ to C60 [3, 4]. For example, bis(trimethylsilylmethyl) sulfoxide in o-dichlorobenzene at 110°C gives rise to thiocarbonyl ylide which adds to C60 with formation of dihydrothieno[3′,4′ : 1,9](C60-Ih)[5,6]fullerene [3]. Catalytic procedures for the synthesis of dihydrothieno[3′,4′ : 1,9](C60-Ih)[5,6]fullerenes have not been reported.