Nickel‐Catalyzed 1,1‐Difluoroethylation of (Hetero)aryl Halides with 1,1‐Difluoroethyl Chloride (CH₃CF₂Cl)

Abstract

1,1‐Difluoroethylated aromatic compounds are of increasing importance in agrochemicals and pharmaceuticals. The direct introduction of difluoroethyl (CF2CH3) group(s) onto aromatic rings using CH3CF2Cl, an inexpensive and available raw material, still remains a great challenge because of the relatively inert C−Cl bond of CH3CF2Cl. Herein, we disclose a nickel‐catalyzed 1,1‐difluoroethylation of (hetero)aryl halides with CH3CF2Cl. The reaction exhibits good functional‐group tolerance and is regarded as a practical method for synthesis of (1,1‐difluoroethyl)arenes.

Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Chlorides with Primary Alkyl Chlorides

“…While the homodimerization of alkyl chlorides and aryl chlorides has been reported, no general cross-selective approach has yet been found . Recently, Zhang reported couplings of a variety of aryl chlorides, but only with an excess of ClCF 2 R reagents . Several groups have reported on the coupling of aryl chlorides with alkyl bromides or tertiary alkyl oxalate esters .…”