Palladium-catalyzed generation of CO from formic acid for alkoxycarbonylation of internal alkenes involves a PTSA-assisted NH–Pd mechanism: a DFT mechanistic study

DFT calculations have been performed to find the mechanism of the alkyloxycarbonylation of an internal alkene with HCOOH catalyzed by a palladium complex with P,N hemilabile ligands. Four different cycles have been explored in detail, and a plausible catalytic cycle involves the decomposition of HCOOH/HCOOMe to CO, internal alkene isomerization, terminal alkene insertion, CO migratory insertion and methanolysis. It is shown that decomposition and isomerization processes involve a cooperative P,N hemilabile ligand and Pd(0) (NH–Pd) rather than the Pd(II) hydride (Pd–H) mechanism. Intriguingly, the simultaneous presence of PTSA acts as a hydrogen shuttle (H-shuttle), assisting CO generation and methanolysis. With such a mechanism, the rate-determining transition state corresponds to internal alkene isomerization, which is consistent with the experimental observation that isomerization was the slow step in this process. The back-bonding between palladium and olefin and rapid hydrogen transfer in the presence of a PTSA H-shuttle are responsible for the moderate barriers. In addition, a careful study of the solvent effect indicates that polar solvents, which are capable of hydrogen bonding, can promote the catalytic reactions. Mechanistic insights gained by this theoretical study have not only rationalized the experimental observations well but also have implications for new reaction development.