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Mechanistic Studies of Pd(II)-Catalyzed E/Z Isomerization of Unactivated Alkenes: Evidence for a Monometallic Nucleopalladation Pathway

preprint
submitted 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.

Funding

NIH-R35GM125052

Honjo International Scholarship

Hearst Foundation Summer Internship

History

Email Address of Submitting Author

keary@scripps.edu

Institution

The Scripps Research Institute

Country

USA

ORCID For Submitting Author

0000-0003-2767-6556

Declaration of Conflict of Interest

No conflict of interest to declare.

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