Open AccessMechanistic Studies of Pd(II)-Catalyzed E/Z Isomerization of Unactivated Alkenes: Evidence for a Monometallic Nucleopalladation Pathway
Author(s) -
Rei Matsuura,
Malkanthi K. Karunananda,
Mingyu Li,
Nhi Nguyen,
Donna G. Blackmond,
Keary M. Engle
Publication year - 2021
Publication title -
acs catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 4.898
H-Index - 198
ISSN - 2155-5435
DOI - 10.1021/acscatal.1c00783
Subject(s) - isomerization , chemistry , catalysis , amide , reaction mechanism , conjugated system , stereochemistry , photochemistry , combinatorial chemistry , organic chemistry , polymer
Pd(II)-catalyzed E/Z isomerization of alkenes is a common process-yet its mechanism remains largely uncharacterized, particularly with non-conjugated alkenes. In this work, the mechanism of Pd(II)-catalyzed E/Z isomerization of unactivated olefins containing an aminoquinoline-based amide directing group is probed using in situ kinetic analysis, spectroscopic studies, kinetic modeling, and DFT calculations. The directing group allows for stabilization and monitoring of previously undetectable intermediates. Collectively, the data are consistent with isomerization occurring through a monometallic nucleopalladation mechanism.