To obtain highly effective antifouling coatings, a series of functional ternary copolymers grafted with short fluoroalkyl or perfluoropolyether modified fluorinated aromatic side chains and cross-linkable functional groups were prepared via radical polymerization. Nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR), gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) were used to characterize the fluoropolymers. The surface properties of the fluoropolymer coatings on cotton fabric, aluminum plates and glass slides were studied. The results indicate that the fluoropolymers show good thermal stabilities (Td > 303 °C), and the hydrophobicity of the fluoropolymer coatings was increased with the increase of fluorinated monomer content (water contact angle on cotton fabric was up to 144°). The antifouling characteristics were investigated by Escherichia coli and Staphylococcus aureus attachment studies. The fluoropolymers exhibited excellent antibacterial activity against E. coli and S. Aureus. The fluoropolymers might be used as promising environmentally benign marine antifouling coating materials due to their high thermal stability, hydrophobicity and antifouling effect.

•A hydrochlorofluorocarbon (HCFC) is used to synthesize 2,2,2-trifluoroethyl diynes.•The C–C bond formation is promoted by copper and ethanolamine.•Two examples of converting the diynes to heterocycles are demonstrated.Copper-mediated reaction of terminal 1,3-diynes with 1,1-dichloro-2,2,2-trifluoroethane (CF3CHCl2) using ethanolamine as ligand gave trifluoroethylated unsymmetrical 1,3-diynes in moderate to good yields. The reaction were carried out under mild conditions, and were easy to operate. Aryl groups with weak electron-withdrawing group or electron-donating group, and alkyl substitutents at terminal 1,3-diynes were tolerated. Synthesis of a trifluoroethylated conjugated triyne by using this method was demonstrated. Further transformation of the trifluoroethylated unsymmetrical 1,3-diyne to provide trifluoroethyl-substituted 1,2,3-triazole and isoxazole as application examples were successfully realized.

A novel strategy was developed to synthesize fluorinated 2-(pyridin-2-yl) alkylamines via condensation of 2-alkylpyridines and chiral fluoromethyl N-tert-butyl sulfinyl imines with good diastereo-control and good chemical yields. The chiral N-tert-butyl sulfinyl auxiliary can be easily removed under mild acidic condition at room temperature. The application of this strategy was demonstrated in the synthesis of a fluorine-containing pesticide candidate.

•This review covers compounds with a CF bond, CF2 or CF3.•Various organic compounds are synthesized through CF bond activation.•Aliphatic fluorides could be activated by Lewis acid, Brønsted superacids or hydrogen bonding.•The cleavage of CF bond could be mediated by transition-metal or rare earth metal.•Dehydrofluorination by a base or SN2′ displacement by a nucleophile could be a method for leaving of a fluoride.CF bond activation of aliphatic fluorides provides new methodologies for synthesis of new fluorinated building blocks as well as versatile non-fluorinated products. This review covers the recent CF bond cleavage examples and further transformation of compounds bearing with an aliphatic fluoride, difluoromethylene group or trifluoromethyl groups. The methods to activate a CF bond include activation by Lewis acid, Brønsted superacids and hydrogen bonding, and mediation by transition-metals and rare earth metals. Partial reduction of trifluoromethyl group through a single electron transfer (SET) process can provide the compounds with less fluorine. Bases are often used for the elimination of hydrofluoride. SN2′ displacement is also an important method for transformation of monofluorinated, difluorinated and trifluorinated olefins to various synthetically interesting molecules.

A convenient and practical method for the asymmetric synthesis of trifluoromethylated aziridines was developed. The reactions of sulfur ylide with (S)-N-tert-butanesulfinyl ketimines gave trifluoromethylated aziridines 3 in moderate to excellent yields (45–93%) and good diastereoselectivities (86:14 to >99:1 dr). The synthetic application of these aziridines was examined through the acidic deprotection of the sulfinyl group and ring-opening reaction with dimethylsulfonium methylide to afford trifluoromethylated cyclopropylamine and α-trifluoromethylallylamine in 80% and 67% yields, respectively.

Stereoselective approach for preparation of α-difluoromethyl α-propargylamines has been developed. 1,2-Addition of lithium acetylides to diverse chiral difluoromethylated (S)-N-tert-butanesulfinyl ketimines by using Ti(OiPr)4 as catalyst and THF as solvent afforded N-tert-butanesulfinamides in good to excellent yields (51–93%) and good diastereoselectivities (dr. 85:15 to 93:7). The N-tert-butanesulfinyl group can be readily cleaved under mild acidic condition (4 mol/L HCl in dioxane) to provide the corresponding α-difluoromethyl α-propargylamine in excellent yields (90–95%).

The Henry (nitroaldol) reaction of fluorinated nitro compounds with various aromatic aldehydes and a fluorinated aliphatic aldehyde to give β-fluoro-β-nitroalcohols which bearing a fluorinated quaternary carbon center was reported. The relative configuration of the major diastereoisomer of 2-fluoro-2-nitro-1-(4-nitrophenyl)-3-phenylpropanol (5bf) was determined by X-ray single crystal analysis.Graphical abstractHenry reaction of α-fluoro nitro compounds with various aldehydes gave fluorinated nitroalcohols in moderate to good yields.Highlights► An organocatalytic Henry reaction of fluoro nitro compounds was described. ► β-Fluoro-β-nitroalcohols bearing a fluorinated quaternary carbon center were obtained. ► The relative configurations of products were determined using X-ray and NMR analysis.

Treatment of chiral N-tert-butyl sulfinylimines with ethyl bromofluoroacetate in the presence of activated Zn dust in THF afforded the α-fluoro-β-amino acid derivatives in good yields (70–86%) and moderate diastereoselectivity (66:34–92:8).

A convenient and practical method for the preparation of enantiomerically pure α-trifluoromethylated α-propargylamines is described. A range of enantiopure α-trifluoromethylated α-propargyl sulfinamides were obtained by the addition of lithium acetylides generated in situ with n-BuLi and terminal alkynes to diverse chiral CF3-substituted (S)-N-tert-butanesulfinyl ketimines in moderate to excellent yields (56–97%) and with uniformly excellent diastereoselectivities (>99:1) by using Ti(OiPr)4 as the catalyst and THF as the polar solvent. Enantiomerically pure α-trifluoromethylated α,α-dibranched propargyl amines were then readily obtained in excellent yields (87–97%) by acidic cleavage of the tert-butanesulfinyl group.(SS,2R)-(+)-N-(1,1,1-Trifluoro-2,4-diphenylbut-3-yn-2-yl)-2-methylpropanesulfinamideC20H20F3NOS[α]D23=+339.2 (c 1.0, CHCl3)Source of chirality: (Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2R)(SS,R)-(+)-N-(4-Cyclopropyl-1,1,1-trifluoro-2-(4-methoxyphenyl)but-3-yn-2-yl)-2-methylpropanesulfinamideC18H22F3NO2S[α]D23=+387.4 (c 1.0, CHCl3)Source of chirality: (Ss)-N-tert-tert-butanesulfinamideAbsolute configuration: (SS,2R)(SS,R)-(+)-N-(2-(4-Chlorophenyl)-1,1,1-trifluorooct-3-yn-2-yl)-2-methylpropanesulfinamideC19H23ClF3NOS[α]D28=+221.0 (c 0.5, CHCl3)Source of chirality: (Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2R)(SS,S)-(+)-N-(2-(4-Chlorophenyl)-1,1,1-trifluorobut-3-yn-2-yl)-2-methylpropanesulfinamideC14H15ClF3NOS[α]D28=+47.0 (c 0.43, CHCl3)Source of chirality: (Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2S)(SS,R)-(+)-N-(3-(Trifluoromethyl)-1-(trimethylsilyl)non-1-yn-3-yl)-2-methylpropanesulfinamideC17H32F3NOSSi[α]D24=+79.8 (c 1.0, CHCl3)Source of chirality: (Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2R)(R)-(+)-4-Cyclopropyl-1,1,1-trifluoro-2-phenylbut-3-yn-2-amineC13H12F3N[α]D29=+32.4 (c 1.0, CHCl3)Source of chirality: (Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2R)(R)-(+)-1,1,1-Trifluoro-2-(4-methoxyphenyl)-4-(trimethylsilyl)but-3-yn-2-amineC14H18F3NOSi[α]D27=+2.0 (c 0.49, CHCl3)Source of chirality: (Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2R)(R)-(+)-1-Cyclopropyl-3-(trifluoromethyl)non-1-yn-3-amineC13H20F3N[α]D29=+36.6 (c 0.42, CHCl3)Source of chirality: ((Ss)-N-tert-butanesulfinamideAbsolute configuration: (SS,2R)