O-Trifluoromethylation of Phenols: Access to Aryl Trifluoromethyl Ethers by O-Carboxydifluoromethylation and Decarboxylative Fluorination.

A new strategy for the synthesis of aryl trifluoromethyl ethers (ArOCF3) by combining O-carboxydifluoromethylation of phenols and subsequent decarboxylative fluorination is reported. This protocol allows easy construction of functionalized trifluoromethoxybenzenes and trifluoromethylthiolated arenes (ArSCF3) in moderate to good yields. Moreover, it utilizes accessible and inexpensive reagents sodium bromodifluoroacetate and SelectFluor II and, thus, is practical for O-trifluoromethylation of phenols. The potential application of this method is demonstrated with the preparation of a plant-growth regulator, Flurprimidol.

Copper-Catalyzed Trifluoromethylation of Polysubstituted Alkenes Assisted by Decarboxylation.

An efficient copper-catalyzed trifluoromethylation of polysubstituted alkenes assisted by decarboxylation of ß,γ-unsaturated carboxylic acids has been achieved. The reaction provides a general method to construct allylic and vinylic CF3-substituted compounds under mild conditions.

Fluoroalkylative aryl migration of conjugated N-arylsulfonylated amides using easily accessible sodium di- and monofluoroalkanesulfinates.

Fluorinated sulfinate salts RfSO2Na (Rf = CF2H, CF2Ph, and CH2F) have been prepared via NaBH4-mediated reduction of the corresponding benzo[d]thiazol-2-yl sulfones, and their synthetic application as di- and monofluoroalkyl radical precursors is demonstrated in the silver-catalyzed cascade fluoroalkylation/aryl migration/SO2 extrusion of conjugated N-arylsulfonylated amides.

Copper-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3 via C-F bond cleavage.

A novel Cu-catalyzed gem-difluoroolefination of diazo compounds is described. This transformation starts from readily available TMSCF3 and diazo compounds, via trifluoromethylation followed by C-F bond cleavage, to afford the desired 1,1-difluoroalkene products.

Copper-catalyzed di- and trifluoromethylation of α,ß-unsaturated carboxylic acids: a protocol for vinylic fluoroalkylations.

Dual action: the Lewis acid CuF(2) ⋅2 H(2)O efficiently catalyzes the reaction between electrophilic fluoroalkylating agents and α,ß-unsaturated carboxylic acids by dually activating both reactants, thus affording di- and trifluoromethyl alkenes in high yields with excellent E/Z selectivity.