Effect of α-Substitution on the Reactivity of C(sp³)-H Bonds in Pd⁰-Catalyzed C-H Arylation.

ABSTRACT: We report mechanistic studies on the reactivity of different α-substituted C(sp³)-H bonds, -CH_nR (R = H, Me, CO₂Me, CONMe₂, OMe, and Ph, as well as the cyclopropyl and isopropyl derivatives -CH(CH₂)₂ and -CHMe₂) in the context of Pd⁰-catalyzed C(sp³)-H arylation. Primary kinetic isotope effects, k_H/k_D, were determined experimentally for R = H (3.2) and Me (3.5), and these, along with the determination of reaction orders and computational studies, indicate rate-limiting C-H activation for all substituents except when R = CO₂Me. This last result was confirmed experimentally (k_H/k_D ∼ 1). A reactivity scale

SUBMITTER: Wheatley M 

PROVIDER: S-EPMC10563019 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature