Faculty Publication: Palladium-Catalyzed γ,γ′-Diarylation of Free Alkenyl Amines

John L Payton, Visiting Assistant Professor of Chemistry, has published an article, “Palladium-Catalyzed γ,γ′-Diarylation of Free Alkenyl Amines” in the June 2021 issue of the Journal of the American Chemical Society with co-authors Vinod G. Landge, Aaron J. Grant, Yu Fu, Allison Rabon, and Michael Young.

Image from Journal of the American Chemical Society

Abstract

The direct difunctionalization of alkenes is an effective way to construct multiple C-C bonds in one-pot using a single functional group. The regioselective dicarbofunctionalization of alkenes is therefore an important area of research to rapidly obtain complex organic molecules. Herein, we report a palladium-catalyzed γ,γ’-diarylation of free alkenyl amines through interrupted chain walking for the synthesis of Z-selective alkenyl amines. Notably, while 1,3-dicarbofunctionalization of allyl groups is well precedented, the present disclosure allows 1,3-dicarbofunctionalization of highly substituted allylamines to give highly Z-selective trisubsubstituted olefin products. This cascade reaction operates via an unprotected amine-directed Mizoroki-Heck (MH) pathway featuring a β-hydride elimination to selectively chain walk to furnish a new terminal olefin which then generates the cis-selective alkenyl amines around the sterically crowded allyl moiety. This operationally simple protocol is applicable to a variety of cyclic, branched, and linear secondary and tertiary alkenylamines, and has a broad substrate scope with regard to the arene coupling partner as well. Mechanistic studies have been performed to help elucidate the mechanism, including the presence of a likely unproductive side C-H activation pathway.

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