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Updated: Jul 25, 2025

Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
Reductive Catalytic Difluorocarbene Transfer via Palladium Catalysis
Xue-Ying Zhang1, Shi-Ping Sun1, Yue-Qian Sang1
1Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
A novel palladium-catalyzed reaction efficiently transfers difluorocarbene from chlorodifluoromethane to form difluoromethylated arenes. This method offers a convenient and functional-group-tolerant approach for synthesizing valuable fluorinated compounds.
Area of Science:
- Organic Chemistry
- Organometallic Chemistry
- Fluorine Chemistry
Background:
- Difluorocarbene is a versatile but challenging reagent in organic synthesis.
- Existing methods for difluorocarbene transfer often require specialized precursors or harsh conditions.
Purpose of the Study:
- To develop a novel palladium-catalyzed reductive difluorocarbene transfer reaction.
- To utilize chlorodifluoromethane as a cost-effective difluorocarbene precursor.
- To enable the synthesis of difluoromethylated (hetero)arenes with high functional group tolerance.
Main Methods:
- Palladium-catalyzed coupling reaction.
- Utilizing chlorodifluoromethane (ClCF2H) as the difluorocarbene source.
- Employing aryl halides/triflates and proton sources as substrates.
Main Results:
- Successful development of a new difluorocarbene transfer mode.
- Efficient synthesis of diverse difluoromethylated (hetero)arenes.
- Demonstrated high functional group tolerance and synthetic convenience.
- Uncovered an unexpected Pd(0/II) catalytic cycle involving a palladium(0) difluorocarbene intermediate.
Conclusions:
- The developed method provides a practical and efficient route to difluoromethylated compounds.
- The use of chlorodifluoromethane offers an economical and accessible precursor.
- The mechanistic study elucidated a novel Pd(0/II) catalytic cycle for reductive difluorocarbene transfer.
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