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

Christopher J. Evoniuk; Gabriel Dos Passos Gomes; Michelle Ly; Frankie D. White; Igor V. Alabugin

doi:10.1021/acs.joc.7b00262

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

Christopher J. Evoniuk, Gabriel Dos Passos Gomes, Michelle Ly, Frankie D. White, Igor V. Alabugin

Research output: Contribution to journal › Article › peer-review

46 Scopus citations

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.

Original language	English
Pages (from-to)	4265-4278
Number of pages	14
Journal	Journal of Organic Chemistry
Volume	82
Issue number	8
DOIs	https://doi.org/10.1021/acs.joc.7b00262
State	Published - Apr 21 2017
Externally published	Yes

Funding

This study was supported by the National Science Foundation (Grant CHE-1465142). We are also grateful to NSF XSEDE (TG-CHE160006) and RCC FSU for computational resources. G.d.P.G. is grateful to IBM for the 2016 IBM Ph.D Scholarship.

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Evoniuk, C. J., Gomes, G. D. P., Ly, M., White, F. D., & Alabugin, I. V. (2017). 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. Journal of Organic Chemistry, 82(8), 4265-4278. https://doi.org/10.1021/acs.joc.7b00262

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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.",

author = "Evoniuk, \{Christopher J.\} and Gomes, \{Gabriel Dos Passos\} and Michelle Ly and White, \{Frankie D.\} and Alabugin, \{Igor V.\}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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day = "21",

doi = "10.1021/acs.joc.7b00262",

language = "English",

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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. / Evoniuk, Christopher J.; Gomes, Gabriel Dos Passos; Ly, Michelle et al.
In: Journal of Organic Chemistry, Vol. 82, No. 8, 21.04.2017, p. 4265-4278.

Research output: Contribution to journal › Article › peer-review

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T2 - Quinolines from Reactions of o-Alkenylarylisonitriles with Aryl, Alkyl, and Perfluoroalkyl Radicals

AU - Evoniuk, Christopher J.

AU - Gomes, Gabriel Dos Passos

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AB - 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.

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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

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