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Enynones are powerful synthons for constructing furan derivatives in the presence of transition metal catalysts. Unlike the conventional intramolecular nucleophilic attack with the activation of coinage metals, we propose that enynones undergo an oxidative cyclization process with a Pd(0) species. The full catalytic cycle involves oxidative cyclization, isocyanide insertion, and reductive elimination, which was supported by DFT calculations. Geometric and electronic analyses confirmed the oxidative cyclization process, which proceeds VIA a Pd(II) intermediate.

Graphical abstract: Oxymetalation or oxidative cyclization? mechanism of Pd-catalyzed annulation of enynones

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