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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.

Authors
  • Jasiński, Radomir1
  • 1 Department of Organic Chemistry, Cracow University of Technology, Poland. Electronic address: [email protected]. , (Poland)
Type
Published Article
Journal
Journal of molecular graphics & modelling
Publication Date
Jan 01, 2020
Volume
94
Pages
107461–107461
Identifiers
DOI: 10.1016/j.jmgm.2019.107461
PMID: 31629187
Source
Medline
Keywords
Language
English
License
Unknown

Abstract

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. Copyright © 2019 Elsevier Inc. All rights reserved.

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