Transforming cyclopropanes to enamides via σ-C-C bond eliminative borylation.

ABSTRACT: Recent strides in C-H borylation have significantly expanded our toolkit for the preparation of organoboronates. Nevertheless, avenues alternative to obtain these compounds via σ-C-C cleavage, thereby facilitating molecular scaffold editing, remain scarce. Several methodologies have been proposed for hydroboration of cyclopropanes by activating C-C bonds, conventionally relying on noble and hazardous metal catalysts to control reaction outcomes. Here, we present a strategy for crafting stereochemically precise γ-borylenamides through ring-opening of cyclopropanes avoiding any metallic entities. Boryl species, generated through a ternary reaction with BCl₃, cyclopropanes, and a tertiary amine, selectively undergo C-C bond eliminative borylation under the directing of N-acyl group, thereby ensuring enhanced selectivity and efficiency along the reaction pathway. Such inherently stereoconvergent approach accommodates precursors of diverse geometries, including cis/trans isomeric blends.

SUBMITTER: Kang S 

PROVIDER: S-EPMC11350172 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature