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Mechanistic Studies of Pd(II)-Catalyzed E/Z Isomerization of Unactivated Alkenes: Evidence for a Monometallic Nucleopalladation Pathway
preprintsubmitted on 06.11.2020, 21:33 and posted on 09.11.2020, 12:05 by Rei Matsuura, Malkanthi Karunananda, Mingyu Liu, Nhi Nguyen, Donna Blackmond, Keary Engle
Pd(II)-catalyzed E/Z isomerization of alkenes is a common process—yet is 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.