Roles of Iron Complexes in Catalytic Radical Alkene Cross-Coupling: A Computational and Mechanistic Study.

ABSTRACT: A growing and useful class of alkene coupling reactions involve hydrogen atom transfer (HAT) from a metal-hydride species to an alkene to form a free radical, which is responsible for subsequent bond formation. Here, we use a combination of experimental and computational investigations to map out the mechanistic details of iron-catalyzed reductive alkene cross-coupling, an important representative of the HAT alkene reactions. We are able to explain several observations that were previously mysterious. First, the rate-limiting step in the catalytic cycle is the formation of the reactive Fe-H intermediate, elucidating the importance of the choice of reductant. Second, the success of the catalytic system is attributable to the exceptionally weak (17 kcal/mol) Fe-H bond, which performs irrever

SUBMITTER: Kim D 

PROVIDER: S-EPMC6953484 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature