Airat R. Tuktarov

1H and 13C NMR chemical shift assignments of spiro-cycloalkylidenehomo- and methanofullerenes by the DFT-GIAO method.

The 1H and 13C NMR chemical shifts of spiro‐cycloalkylidene[60]fullerenes were assigned using experimental NMR data and the Density Functional Theory (DFT)–Gauge Independence Of Atomic Orbitals method (GAIO) calculation method in the Perdew Burke Ernzerhof (PBE)/3z approach. The calculated values of the 13C NMR chemical shifts adequately reproduce the experimental values at this quantum chemistry approach. Similar assignments will be helpful for 13C NMR spectral analysis of homo‐ and methano[60]fullerene derivatives for structure elucidation and to determine the influence of fullerene frames on substituents and the influence of substituents on fullerene cores. Copyright

Catalytic cycloaddition of diazoalkanes to fullerene C60

Cycloaddition to fullerene C60 of monosubstituted diazomethanes generated in situ by oxidation of aldehyde hydrazones in the presence of Pd(acac)2-2 PPh3-4 Et3Al as catalytic system resulted in selective formation of homofullerenes in which the alkyl substituent is located above the plane of the five-membered ring in C60. Under analogous conditions, unsymmetrical disubstituted diazomethanes generated from the corresponding ketone hydrazones gave rise to mixtures of stereoisomeric 5,6-open adducts.

Homo‐ and methano[60]fullerenes with chiral attached moieties – 1H and 13C NMR chemical shift assignments and diastereotopicity effects

1H and 13C NMR chemical shift predictions of homo‐ and methano[60]fullerenes containing chiral centers in attached fragment were made using the two‐dimensional NMR technique (HH COSY, 1H–13C HSQC and HMBC) and the quantum chemistry GIAO calculation method in the PBE/3ζ approach. The influence of a chiral substituent on the 13C chemical shifts of diastereotopic fullerene carbons was estimated by comparing the calculated and experimental 13C NMR spectra. The resonances of the fullerene carbons in α‐, β‐ and δ‐positions relative to the position of the substituent exhibit the greatest diastereotopic splitting. Copyright

Catalytic cyclopropanation of fullerene[60] with diazomethane

The selective cyclopropanation of C60-fullerene with diazomethane was performed under the catalysis with Pd(acac)2, and individual 5,6-open and 6,6-closed cycloadducts were obtained.

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.

Diastereotopic splitting in the 13C NMR spectra of sulfur homofullerenes and methanofullerenes with chiral fragments.

Using gauge‐invariant atomic orbital PBE/3ζ quantum chemistry approach, 13C NMR chemical shifts and diastereotopic splittings of sp2 fullerenyl carbons of a number of sulfur homofullerenes and methanofullerenes have been predicted and discussed. An anisochrony of fullerene carbons is caused by a chiral center of attached moieties. Clearly distinguishable diastereotopic pairs (from 8 to 11) of fullerenyl carbons of homofullerenes were observed. Unambiguous assignments of 13C NMR chemical shifts were performed, and diastereotopic splittings of methanofullerenes were observed for α, β and γ to a functionalization site. Copyright

Catalytic cycloaddition of diazoalkanes with heterocyclic substituents to fullerene C60

Methanofullerenes were directly synthesized under mild conditions by cycloaddition to fullerene C60 of diazoalkanes generated in situ by oxidation of ketone hydrazones containing a heterocyclic fragment with manganese(IV) oxide in the presence of the catalytic system Pd(acac)2-2 PPh3-4 Et3Al.

Cycloaddition of cage and polycyclic diazo compounds to C60 fullerene catalyzed by Pd(acac)2-2PPh3-4Et3Al

Spirohomofullerenes were synthesized by cycloaddition of cage and polycyclic diazoalkanes generated in situ by oxidation of hydrazones of camphor, 2-adamantanone, and cholestane-3-one to C60 fullerene in the presence of the Pd(acac)2-2PPh3-4Et3Al three-component catalyst. It was found that the spiro-homofullerenes obtained from hydrazones of 2-adamantanone and cholestane-3-one and C60 fullerene do not undergo thermal isomerization to the corresponding spiro-methanofullerenes.

Catalytic hydroamination of fullerene C60 with primary and secondary amines

Catalytic 1,2-hydroamination of fullerene C60 with primary and secondary amines in the presence of Ti, Zr, and Hf complexes gave the corresponding alkyl-, aryl-, and hetarylaminodihydrofullerenes.

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.