title: Coupling Radical Homoallylic Expansions with C-C Fragmentations for the Synthesis of Heteroaromatics: Quinolines from Reactions of o-Alkenylarylisonitriles with Aryl, Alkyl, and Perfluoroalkyl Radicals.
abstract: Selective 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. Computational analysis of the homoallyic expansion potential energy surface reveals that the indirect 5-exo/3-exo/retro-3-exo path is faster than the direct 6-endo-trig closure, revealing the general exo-preference for the cyclization processes.
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306-4390, United States.
authors.forename: Christopher J
authors.identifier: 0000-0002-9595-4004
authors.initials: CJ
authors.lastname: Evoniuk
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306-4390, United States.
authors.forename: Gabriel Dos Passos
authors.identifier: 0000-0002-8235-5969
authors.initials: GDP
authors.lastname: Gomes
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306-4390, United States.
authors.forename: Michelle
authors.initials: M
authors.lastname: Ly
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306-4390, United States.
authors.forename: Frankie D
authors.initials: FD
authors.lastname: White
authors.affiliation: Department of Chemistry and Biochemistry, Florida State University , Tallahassee, Florida 32306-4390, United States.
authors.forename: Igor V
authors.identifier: 0000-0001-9289-3819
authors.initials: IV
authors.lastname: Alabugin