A new insight on the molecular mechanism of the reaction between (Z)-C,N-diphenylnitrone and 1,2-bismethylene-3,3,4,4,5,5-hexamethylcyclopentane / Radomir Jasiński // Journal of Molecular Graphics and ... więcej

A new insight on the molecular mechanism of the reaction between (Z)-C,N-diphenylnitrone and 1,2-bismethylene-3,3,4,4,5,5-hexamethylcyclopentane / Radomir Jasiński // Journal of Molecular Graphics and Modelling [Dokument elektroniczny]. – 2020, Vol. 94, 5 s. : schem., tab., wykr. – Tryb dostępu: https://www.sciencedirect.com/science/article/pii/S1093326319306345. – Oznaczenie ref./art.: 107461. – Bibliogr. 28 poz., Abstr. – doi: 10.1016/j.jmgm.2019.107461. – ISSN 1093-3263

The molecular reaction mechanism of (Z)-C,N-diphenylnitrone and 1,2-bismethylene-3,3,4,4,5,5-hexamethylcyclopentane was verified, based on M062x/6-311 + G(d) quantumchemical calculations. It was shown ... więcej

The molecular reaction mechanism of (Z)-C,N-diphenylnitrone and 1,2-bismethylene-3,3,4,4,5,5-hexamethylcyclopentane was verified, based on M062x/6-311 + G(d) quantumchemical calculations. It was shown that, contrary to what was postulated in earlier reports, this reaction process occurs without the intervention of a biradical intermediate. In particular, [3 + 2] cycloadducts are formed by a one-step non-polar reaction. The most likely scenario for the formation of the [3 + 4] adduct is the 1,3-sigmatropic rearrangement of the [3 + 2] adduct, or the 1,2-sigmatropic rearrangement of the Diels-Alder labile adduct. It has been shown that this mechanism can be generalised for reactions involving a broader group of 2,3-substituted buta-1,3-diene analogues.