The E/Z isomerization of internal alkenes under palladium catalysis is a fundamental reaction that has been known for >50 years. The mechanism remains poorly understood, particularly in the case of non-conjugated alkene substates and palladium(II) carboxylate catalysts (e.g., Pd(OAc)2). To clarify this mechanistic puzzle, Rei (a joint student with the Blackmond lab), Malkanthi, Mingyu, and Nhi (a former high school intern), combined insights from reaction kinetics, in situ NMR, isotope labeling experiments, and computation. The data ruled out several other mechanistic hypotheses proposed in the literature and pointed to a monometallic nucleopalladation pathway. Check out the accepted paper in ACS Catalysis. Congrats to the whole team!
For a link to the paper, click here: https://pubs.acs.org/doi/10.1021/acscatal.1c00783
The work first appeared back in November. Check out the pre-print here: https://chemrxiv.org/articles/preprint/Mechanistic_Studies_of_Pd_II_-Catalyzed_E_Z_Isomerization_of_Unactivated_Alkenes_Evidence_for_a_Monometallic_Nucleopalladation_Pathway/13194932