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Non-pericyclic cycloaddition of gem-difluorosubstituted azomethine ylides to the C[double bond, length as m-dash]O bond: computational study and synthesis of fluorinated oxazole derivatives

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Abstract

The cycloaddition of arenecarbaldehydes and α,α,α-trifluoroacetophenones with gem-difluoro-substituted azomethine ylides, generated from N-benzhydrylideneamines and difluorocarbene, occurs regioselectively to give, after hydrolysis, oxazolidin-4-ones. The primary cycloadducts of trifluoroacetophenones, 4,4-difluoro-5-trifluoromethyloxazolidine derivatives, are sufficiently stable to be isolated in reasonable to excellent yields. The results of correlation analysis and DFT calculations reveal a non-pericyclic step-wise mechanism of the reaction. The replacement of the two geminal hydrogen atoms in the azomethine ylide intermediate for fluorine atoms results in a dramatic change in the reaction mechanism from pericyclic to step-wise, proceeding via a zwitterion-like transition state in which no C–O bonding is observed.

Graphical abstract: Non-pericyclic cycloaddition of gem-difluorosubstituted azomethine ylides to the C [[double bond, length as m-dash]] O bond: computational study and synthesis of fluorinated oxazole derivatives

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Publication details

The article was received on 01 Mar 2017, accepted on 04 May 2017 and first published on 04 May 2017


Article type: Paper
DOI: 10.1039/C7OB00521K
Citation: Org. Biomol. Chem., 2017, Advance Article
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    Non-pericyclic cycloaddition of gem-difluorosubstituted azomethine ylides to the C[double bond, length as m-dash]O bond: computational study and synthesis of fluorinated oxazole derivatives

    K. R. Gaisina, A. F. Khlebnikov and M. S. Novikov, Org. Biomol. Chem., 2017, Advance Article , DOI: 10.1039/C7OB00521K

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