Isotope Effects Reveal the Catalytic Mechanism of the Archetypical Suzuki-Miyaura Reaction.

ABSTRACT: Experimental and theoretical ¹³C kinetic isotope effects (KIEs) are utilized to obtain atomistic insight into the catalytic mechanism of the Pd(PPh₃)₄-catalyzed Suzuki-Miyaura reaction of aryl halides and aryl boronic acids. Under catalytic conditions, we establish that oxidative addition of aryl bromides occurs to a 12-electron monoligated palladium complex (Pd-(PPh₃)). This is based on the congruence of the experimental KIE for the carbon attached to bromine (KIE_C-Br = 1.020) and predicted KIE_C-Br for the transition state for oxidative addition to the Pd(PPh₃) complex (1.021). For aryl iodides, the near-unity KIE_C-I of ~1.003 suggests that the first irreversible step in the catalytic cycle precedes ox

SUBMITTER: Joshi C 

PROVIDER: S-EPMC10168682 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature