DFT Investigation of Suzuki-Miyaura Reactions with Aryl Sulfamates Using a Dialkylbiarylphosphine-Ligated Palladium Catalyst.

ABSTRACT: Aryl sulfamates are valuable electrophiles for cross-coupling reactions because they can easily be synthesized from phenols and can act as directing groups for C-H bond functionalization prior to cross-coupling. Recently, it was demonstrated that (1-^tBu-Indenyl)Pd(XPhos)Cl (XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl) is a highly active precatalyst for room-temperature Suzuki-Miyaura couplings of a variety of aryl sulfamates. Herein, we report an in-depth computational investigation into the mechanism of Suzuki-Miyaura reactions with aryl sulfamates using an XPhos-ligated palladium catalyst. Particular emphasis is placed on the turnover-limiting oxidative addition of the aryl sulfamate C-O bond, which has not been studied in detail previously. We show that bide

SUBMITTER: Melvin PR 

PROVIDER: S-EPMC5967261 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature