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Issue 19, 2017
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Changing the path of least resistance, or access to endo-dig products via a sequence of three exo-trig transition states: electronic effects in homoallyic ring expansion cascades of alkenyl isonitriles

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Abstract

Chemoselective addition of radicals to isonitriles can be harnessed for initiating reaction cascades designed to overcome the stereoelectronic restrictions on homoallylic ring expansion in alkyne reactions and to develop a new general route for the preparation of N-heteroaromatics. This method utilizes alkenes as synthetic equivalents of alkynes by coupling homoallylic ring expansion to yield the formal “6-endo” products with aromatization via stereoelectronically assisted C–C bond scission. Detailed computational analysis of the individual steps of the homoallylic expansion sequence maps effects of substituents and structural constraints on this multi-step potential energy surface.

Graphical abstract: Changing the path of least resistance, or access to endo-dig products via a sequence of three exo-trig transition states: electronic effects in homoallyic ring expansion cascades of alkenyl isonitriles

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Publication details

The article was received on 02 Mar 2017, accepted on 03 Apr 2017 and first published on 03 Apr 2017


Article type: Paper
DOI: 10.1039/C7OB00527J
Citation: Org. Biomol. Chem., 2017,15, 4135-4143
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    Changing the path of least resistance, or access to endo-dig products via a sequence of three exo-trig transition states: electronic effects in homoallyic ring expansion cascades of alkenyl isonitriles

    G. D. P. Gomes, C. J. Evoniuk, M. Ly and I. V. Alabugin, Org. Biomol. Chem., 2017, 15, 4135
    DOI: 10.1039/C7OB00527J

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