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Controlling Cyclization Pathways in Palladium(II)-Catalyzed Intramolecular Alkene Hydrofunctionalization via Substrate Directivity

preprint
submitted on 08.04.2020 and posted on 09.04.2020 by Xin Wang, Zi-Qi Li, Binh Khanh Mai, John Gurak, Jessica Xu, Van Tran, Zhen Liu, Zhonglin Liu, Kin Yang, Rong Xiang, Peng Liu, Keary Engle
We report a series of palladium(II)-catalyzed, intramolecular alkene hydrofunctionalization reactions with carbon, nitrogen, and oxygen nucleophiles to form five- and six-membered carbo- and heterocycles. In these reactions, the presence of a proximal bidentate directing group controls the cyclization pathway, dictating the ring size that is generated, even in cases that are disfavored based on Baldwin’s rules and in cases where there is an inherent preference for an alternative pathway. DFT studies shed light on the origins of pathway selectivity in these processes.

Funding

NIH-R35GM125052

NIH-R35GM128779

NSF-DGE-1346837

NSF-ACI-1548562

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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