Exploring the mechanism of the Pd-catalyzed spirocyclization reaction: a combined DFT and experimental study.

ABSTRACT: The mechanism of the palladium-catalyzed spirocyclization of acrylamides has been investigated by density functional theory and experimental studies. The results support a mechanistic pathway that proceeds via oxidative addition, intramolecular carbopalladation, C-H bond activation, and migratory insertion sequence. The M06L/def2-TZVPP//BP86/6-31G(d,p)/LANL2DZ level of theory used and the inclusion of solvent effects provide results in good agreement with the experimental data. The C-H bond activation step proceeds via a concerted outer-sphere metallation deprotonation mechanism that explains the absence of a measurable kinetic isotopic effect. The subsequent intermolecular migratory insertion of arynes is significantly faster than the insertion of internal alkynes. Fu

SUBMITTER: Franzoni I 

PROVIDER: S-EPMC5885594 | biostudies-literature | 2018 Feb

REPOSITORIES: biostudies-literature