Rhodium-Catalyzed Z-Alkenyl 1,3-Migration

Abstract

Strategies for the selective cleavage of inert C-C bonds in tertiary alcohols have been developed. However, a gap remains in Z-alkenyl 1,3-migration through selective C(sp³)-C(Z-alkenyl) bond cleavage. Herein, we report rhodium-catalyzed Z-alkenyl 1,3-migration, which efficiently yields (Z)-γ,δ-unsaturated ketones. The success of the transformation could be attributed to selective C(sp³)-C(Z-alkenyl) bond cleavage. In this study, we disclose that the migration order in this catalytic system is Z-alkenyl, E-alkenyl, and aryl (alkyl), in decreasing reactivity. This catalytic system has the advantages of good functional group compatibility, a wide range of substrates, and mild reaction conditions.