title: 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 "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.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA. alabugin@chem.fsu.edu.
authors.forename: Gabriel Dos Passos
authors.initials: GDP
authors.lastname: Gomes
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Evoniuk
authors.forename: Michelle
authors.initials: M
authors.lastname: Ly
authors.forename: Igor V
authors.initials: IV
authors.lastname: Alabugin