Palladium-Catalyzed ipso-Didefluoroannulation of Allylic gem-Difluorides with Salicylic Acids
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Updated: Jan 14, 2026

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Sheng-Yu Chen1,2, Xue-Qing Wang2, Lu-Ning Tang2
1School of Chemical Engineering and Materials, Changzhou Institute of Technology, Changzhou 213032, China.
Abstract:
A palladium-catalyzed C3-ipso-didefluoroannulation of allylic gem-difluorides with salicylic acids has been developed, proceeding under mild conditions with broad functional group tolerance and enabling late-stage functionalization of bioactive scaffolds. Mechanistic studies reveal a key monofluoroalkene intermediate that undergoes two successive Pd(0)/Pd(II) cycles involving C-F activation and allylic C-O oxidative addition with a formal 1,3-ether migration, thereby reversing both catalyst- and nucleophile-controlled regioselectivities. This strategy not only expands the synthetic utility of allylic gem-difluorides but also establishes a new paradigm for regioselective C-F bond functionalization in transition metal catalysis.
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