Catalytic dicarbofunctionalization of unactivated alkenes is an emerging synthetic method that holds a great promise to furnish a modular, convergent, and expedient route to generate complex molecules rapidly from readily available starting materials. Although a tremendous progress has been made in the field, there is much more research problem yet to be solved. Here, we disclose a transmetalation-initiated Ni(I)-catalyzed regioselective β,δ-vinylarylation of γ,δ-alkenyl a-cyanocarboxylic esters with vinyl triflates and arylzinc reagents. This reaction proceeds via a simple functional group-assisted contraction of six-membered nickellacycles to five-membered nickellacycles to form two new carbon-carbon bonds at the nonclassical homovicinal sites, and provides expeditious access to a wide range of complex aliphatic α-cyanoesters, α-cyanocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoamides, monocarboxylic acids, nitriles and spirolactones. Control, deuterium labeling and crossover experiments indicate that the nickellacycle contraction occurs by β-H elimination followed by hydronickellation on transiently formed alkenes, and that the Ni species are stabilized as Ni-enolates.

Alkene dicarbofunctionalization by metallacycle contraction process

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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