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Updated: May 31, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
General Difluoroalkylation of Unactivated Alkenes Via Allylic Mizoroki-Heck Coupling
Jing Wang1, Zhaoping You1,2, Tiancen Bian3
1Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, P. R. China.
Abstract:
The gem-difluoromethylene (CF2) unit is a privileged motif in medicinal and synthetic chemistry, yet its direct incorporation at the allylic positions of unactivated alkenes remains challenging. Herein, we report a unified palladium-catalyzed strategy for allylic difluoroalkylation that employs readily available chlorodifluoroalkanes (Cl-CF2R) as CF2R radical precursors. This redox-neutral transformation proceeds under mild conditions and converts simple alkenes into allylic CF2R products with high regioselectivity and stereoselectivity. The method accommodates a broad range of CF2R groups, including alkyl, ester, and aryl substituents, and tolerates diverse functional groups and complex molecular scaffolds. Mechanistic studies support radical generation from Cl-CF2R reagents and reveal that the in situ installed gem-difluoromethylene unit guides regioselective β-H elimination from the Pd-(II) intermediate. This protocol provides a general and atom-economical platform for the installation of allylic gem-difluoroalkyl motifs, expanding the accessible chemical space from simple alkene feedstocks.
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