Copper-Mediated Oxidative Chloro- and Bromodifluoromethylation of Phenols.

The first oxidative chloro- and bromodifluoromethylation of phenols with (CH)SiCFX and CuX (X = Cl or Br) in the presence of Selectfluor under mild reaction conditions was developed. This protocol provided a practical and efficient method for the synthesis of a diverse range of biologically valuable and synthetically challenging chloro- and bromodifluoromethyl aryl ethers. Preliminary mechanistic studies suggest that this reaction proceeded through a difluorocarbene-involved oxidative coupling process.

-Trifluoromethoxyphthalimide: A Shelf-Stable Reagent for Nucleophilic Trifluoromethoxylation.

Due to the unique properties of the OCF group, trifluoromethyl ether compounds play an important role in pharmaceuticals and agrochemicals. Recently, considerable attention has been focused on the development of practical and convenient reagents for the direct incorporation of the OCF group into organic compounds. Herein, we reported a new trifluoromethoxylating reagent -trifluoromethoxyphthalimide (Phth-OCF).

Photoredox-Catalyzed and Silane-Mediated Hydrofluoromethylation of Unactivated Alkenes with Fluoroiodomethane in Water.

The first hydrofluoromethylation of unactivated alkenes with fluoroiodomethane and hydrosilanes is developed by merging photoredox catalysis and silane-mediated deiodination processes. The key to the success of this reaction is the use of water as the solvent to enhance the activity of CHF radical toward unactivated alkenes.

Nucleophilic and Radical Heptafluoroisopropoxylation with Redox-Active Reagents.

The heptafluoroisopropyl group (CF(CF ) ) is prevalent in pharmaceuticals and agrichemicals. However, heptafluoroisopropoxylated (OCF(CF ) ) compounds remain largely underexplored, presumably due to the lack of efficient access to these compounds. Herein, we disclose the practical and efficient heptafluoroisopropoxylation reactions through the invention of a series of redox-active N-OCF(CF ) reagents.

Copper and Zinc Copromoted Bromo(chloro)trifluoromethylation of Alkenes and Alkynes with Trifluoromethanesulfonic Anhydride.

The first copper and zinc copromoted trifluoromethylation using trifluoromethanesulfonic anhydride (TfO) as a trifluoromethylating reagent has been developed. The reaction of alkenes or alkynes with TfO in the presence of CuX (X = Br, Cl), Zn powder, and 2,2'-bipyridine affords bromo(chloro)trifluoromethylated products in good yields. CuX plays a dual role as the catalyst and halide source, whereas 2,2'-bipyridine acts as both the activation reagent and ligand.

Oxidative Hydro-, Bromo-, and Chloroheptafluoroisopropylation of Unactivated Alkenes with Heptafluoroisopropyl Silver.

Oxidant-induced three-component hydro-, bromo-, and chloroheptafluoroisopropylation of unactivated alkenes are disclosed. In these reactions, the CF(CF) radical was generated from the oxidation of AgCF(CF). Then the addition of this perfluorinated radical to alkenes, followed by hydrogenation, bromination, or chlorination, gave the corresponding difunctionalized CF(CF)-containing products in high yields.