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Issue 1, 2008
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Molecular rearrangements through thermal [1,3] carbon shifts

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Abstract

Molecular rearrangements through thermal [1,3] carbon shifts, such as vinylcyclopropane-to-cyclopentene and vinylcyclobutane-to-cyclohexene isomerizations, were recognized and exemplified repeatedly from 1960–1964. Serious mechanistic studies of these and related rearrangements over the past 40 years have provided ample grounds for interpreting them as processes taking place by way of conformationally flexible but not statistically equilibrated diradical intermediates. Orbital symmetry theory fails to account for the stereochemical characteristics of [1,3] carbon shifts. For sigmatropic reactions of this class the theory can no longer be retained as a valid basis for mechanistic interpretations, or even as a serious contender for consideration as a mechanistic possibility.

Graphical abstract: Molecular rearrangements through thermal [1,3] carbon shifts

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Publication details

The article was received on 27 Jul 2007 and first published on 11 Oct 2007


Article type: Perspective
DOI: 10.1039/B711494J
Org. Biomol. Chem., 2008,6, 36-47

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    Molecular rearrangements through thermal [1,3] carbon shifts

    J. E. Baldwin and P. A. Leber, Org. Biomol. Chem., 2008, 6, 36
    DOI: 10.1039/B711494J

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