Work

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

Year: 2025

Type: 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=CH2, in which X denotes a phosphorus (P(O)R), silicon (SiR2), sulfur (SO2), 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 sp2 carbons being a key step of catalytic cycle. To the best of our knowledge, this type of metal migration has not been reported previously. 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. Here, the authors report a palladium-catalyzed migratory cyclization of α-bromoalkene derivatives to yield benzoheterocycles.

Source: Nature Communications

DOI: 10.1038/s41467-025-58633-5