Palladium-Catalyzed Oxidation of β-C(sp³)-H Bonds of Primary Alkylamines through a Rare Four-Membered Palladacycle Intermediate.

ABSTRACT: Site-selective functionalizations of C-H bonds are often achieved with a directing group that leads to five- or six-membered metallacyclic intermediates. Analogous reactions that occur through four-membered metallacycles are rare. We report a challenging palladium-catalyzed oxidation of primary C-H bonds β to nitrogen in an imine of an aliphatic amine, a process that occurs through a four-membered palladacyclc intermediate. The success of the reaction relies on the identification, by H/D exchange, of a simple directing group (salicylaldehyde) capable of inducing the formation of this small ring. To gain insight into the steps of the catalytic cycle of this unusual oxidation reaction, a series of mechanistic experiments and density functional theory (DFT) calculations were conducted. The ex

SUBMITTER: Su B 

PROVIDER: S-EPMC11620756 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature