Synthesis of benzoheterocycles by palladium-catalyzed migratory cyclization through an unexpected reaction cascade.

Nat Commun

Inner Mongolia Key Laboratory of Low Carbon Catalysis, Inner Mongolia Key Laboratory of Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, China.

Published: April 2025


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Article Abstract

Migratory functionalization of C-H bonds through metal migration from carbon to carbon under transition metal catalysis is a process of significant academic and industrial interest. Herein, a palladium-catalyzed migratory cyclization of α-bromoalkene derivatives ArXCBr=CH, in which X denotes a phosphorus (P(O)R), silicon (SiR), sulfur (SO), carbon (C(O)), nitrogen (NTs), or oxygen-based moiety, affording various benzoheterocyclic compounds has been developed. Mechanistic investigations have demonstrated that the cyclization reaction proceeds through an unexpected cascade, with trans-1,2-palladium migration between sp carbons being a key step of catalytic cycle. To the best of our knowledge, this type of metal migration has not been reported previously.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11982304PMC
http://dx.doi.org/10.1038/s41467-025-58633-5DOI Listing

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