Issue 19, 2017

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

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 ā€œ6-endoā€ products with aromatization via stereoelectronically assisted Cā€“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

Supplementary files

Article information

Article type
Paper
Submitted
02 Mar 2017
Accepted
03 Apr 2017
First published
03 Apr 2017

Org. Biomol. Chem., 2017,15, 4135-4143

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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