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Issue 32, 2016
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Bent bonds and the antiperiplanar hypothesis – a simple model to rationalize [1,3]-sigmatropic alkyl shifts

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Abstract

The bent bond/antiperiplanar (BBA) hypothesis has been applied to the analysis of [1,3]-sigmatropic alkyl shifts. These thermal rearrangements, for which there is evidence that they proceed through diradical intermediates, can be interpreted by considering their transient allyl radical structures. For the thermolysis of cyclic molecules, the preferred generation of pyramidal allyl radicals in staggered conformations is postulated on the basis of the BBA hypothesis. This accounts for the preference of suprafacial rearrangement pathways as well as the extent of inversion or retention of configuration at the migrating carbons.

Graphical abstract: Bent bonds and the antiperiplanar hypothesis – a simple model to rationalize [1,3]-sigmatropic alkyl shifts

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Publication details

The article was received on 25 May 2016, accepted on 21 Jul 2016 and first published on 21 Jul 2016


Article type: Paper
DOI: 10.1039/C6OB01139J
Citation: Org. Biomol. Chem., 2016,14, 7754-7767
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    Bent bonds and the antiperiplanar hypothesis – a simple model to rationalize [1,3]-sigmatropic alkyl shifts

    G. Deslongchamps and P. Deslongchamps, Org. Biomol. Chem., 2016, 14, 7754
    DOI: 10.1039/C6OB01139J

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