Cine-Substitution of Enolates: Enolate Dance/Coupling of Cycloalkenyl Pivalates by Nickel Catalysis

Abstract

This manuscript describes the development of Ni/dcype-catalyzed enolate dance/coupling reaction of alkenyl pivalates with nucleophiles, resulting in cine-substitution. Pivalates derived 1-tetralone undergo this reaction, to produce C2-functionalized dihydronaphthalenes. The direct utilization of 1-tetralone is also feasible, employing Piv2O to generate the corresponding enol pivalate in situ. Mechanistic investigations including stoichiometric experi-ments, suggest that the reaction proceeds via C–O oxidative addition, nickel 1,2-translocation, and subsequent cou-pling with a nucleophile.

Cine-Substitution of Enolates: Enolate Dance/Coupling of Cycloalkenyl Pivalates by Nickel Catalysis

“…In summary, we have developed a Ni-catalyzed cine -substitution of alkenyl pivalates with various nucleophiles, a process that provides a conceptually novel substituted for synthesizing cyclic alkenes from ketones . Mechanistic studies strongly suggest that this reaction involves a unique nickel-translocation in alkenyl–nickel species.…”