Abstract

Comprehensive SummaryTransition metal‐catalyzed carbometallation of unsaturated hydrocarbons constitutes one of the most efficient synthetic methodologies for the construction of C—C bond. Recently, the incorporation of organometallic reagent with the CO gas as a nucleophilic acyl synthon could enable the acylmetallation reaction, which greatly increases the horizon of carbometallation chemistry. Herein, we report a nickel‐catalyzed regiodivergent acylzincation of o‐cyano cinnamate ester and o‐cyano styrene, in which the cyano moiety intramolecularly captures zinc intermediates to trigger the tandem cyclization process. This protocol features mild conditions, broad substrate scope and excellent functional group tolerance, thus affording a diverse array of highly functionalized carbocyclic compounds.

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