Transition State Asymmetry in C-H Bond Cleavage by Proton-Coupled Electron Transfer.

ABSTRACT: The selective transformation of C-H bonds is a longstanding challenge in modern chemistry. A recent report details C-H oxidation via multiple-site concerted proton-electron transfer (MS-CPET), where the proton and electron in the C-H bond are transferred to separate sites. Reactivity at a specific C-H bond was achieved by appropriate positioning of an internal benzoate base. Here, we extend that report to reactions of a series of molecules with differently substituted fluorenyl-benzoates and varying outer-sphere oxidants. These results probe the fundamental rate versus driving force relationships in this MS-CPET reaction at carbon by separately modulating the driving force for the proton and electron transfer components. The rate constants depend strongly on the pK_a of th

SUBMITTER: Darcy JW 

PROVIDER: S-EPMC7241443 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature