An iron-mediated three-component chlorotrifluoromethylation of both styrenes and aliphatic alkenes has been presented here. This reaction employs ferric chloride (FeCl₃) as the Cl source and the Langlois reagent (CF₃SO₂Na) as the CF₃ source. It provides a convenient pathway towards a wide range of chlorotrifluoromethylated compounds.

Bromodifluoromethylphosphonium bromide was solely used as the precursor of difluorocarbene. Herein, an unprecedented visible-light-induced hydrodifluoromethylation of alkenes with bromodifluoromethylphosphonium bromide using H₂O and THF as hydrogen sources for the synthesis of difluoromethylated alkanes is described. This difluoromethylation is characterized by mild reaction conditions, ready availability of reagents, and excellent functional-group tolerance.

Bromodifluoromethylphosphonium bromide was solely used as the precursor of difluorocarbene. Herein, an unprecedented visible-light-induced hydrodifluoromethylation of alkenes with bromodifluoromethylphosphonium bromide using H₂O and THF as hydrogen sources for the synthesis of difluoromethylated alkanes is described. This difluoromethylation is characterized by mild reaction conditions, ready availability of reagents, and excellent functional-group tolerance.

An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF₃ and nBu₄NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by changing the ratio of AgSCF₃/nBu₄NI. This protocol is tolerant of different functional groups and might be applicable to late-stage trifluoromethylthiolation of alcohols.

An unprecedented reaction for the direct trifluoromethylthiolation and fluorination of alkyl alcohols using AgSCF₃ and nBu₄NI has been developed. The trifluoromethylthiolated compounds and alkyl fluorides were selectively formed by changing the ratio of AgSCF₃/nBu₄NI. This protocol is tolerant of different functional groups and might be applicable to late-stage trifluoromethylthiolation of alcohols.

Aryl trifluoromethyl ethers (ArOCF₃) are prevalent in pharmaceuticals, agrochemicals, and materials. However, methods for the general and efficient synthesis of these compounds are extremely underdeveloped and limited. Herein, we describe a highly efficient and general procedure for the direct O-trifluoromethylation of unprotected phenols through a silver-mediated cross-coupling reaction using CF₃SiMe₃ as the CF₃ source and exogenous oxidants. This novel oxidative trifluoromethylation provides access to a wide range of aryl trifluoromethyl ethers from simple phenols. The mild process was also applied to the late-stage trifluoromethylation of a medicinally relevant compound.

Aryl trifluoromethyl ethers (ArOCF₃) are prevalent in pharmaceuticals, agrochemicals, and materials. However, methods for the general and efficient synthesis of these compounds are extremely underdeveloped and limited. Herein, we describe a highly efficient and general procedure for the direct O-trifluoromethylation of unprotected phenols through a silver-mediated cross-coupling reaction using CF₃SiMe₃ as the CF₃ source and exogenous oxidants. This novel oxidative trifluoromethylation provides access to a wide range of aryl trifluoromethyl ethers from simple phenols. The mild process was also applied to the late-stage trifluoromethylation of a medicinally relevant compound.

A new method for the efficient synthesis of alkynyl trifluoromethyl sulfides was developed. By combining AgSCF₃ and NCS in N,N-dimethylacetamide, an electrophilic active intermediate was produced, which was then treated with a variety of terminal alkynes to afford the corresponding trifluoromethanesulfenylated products in moderate to excellent yields.

A mild and versatile approach for the direct introduction of ethoxycarbonyldifluoromethyl-group to heteroarenes via visible-light photocatalysis has been developed. The new photoredox protocol has enabled the difluoromethylenation of heteroarenes containing a wide range of common functional groups under mild conditions.

A series of novel γ,γ-difluorinated Goniothalamin analogues 4a–4i and 6a–6i were synthesized. The key steps included the construction of C-5 stereocenter adjacent to gem-difluoromethylene group by way of lipase AK catalyzed kinetic resolution, the introduction of aryl group via Stille coupling, and lactonization by 1,5-oxidative cyclization. These γ,γ-difluorinated Goniothalamin analogues 4a–4i and their enantiomers 6a–6i, together with several corresponding γ-monofluorinated Goniothalamin analogues were biologically evaluated against four different cancer cell lines. Compound 7h showed a nearly equivalent potency as the parent (R)-Goniothalamin in the micromolar range. The different fluorine effects between fluoromethylene and gem-difluoromethylene on antitumor activity were discussed through the analysis of bioassay data.

An improved method for the efficient copper-mediated trifluoromethylation of terminal alkynes has been developed. This protocol highlights the convenient access to a variety of aryl-substituted trifluoromethylated alkynes by oxidative trifluoromethylation with two equivalents of TMSCF₃ at room temperature.

Introduction of fluorine atoms or fluorine-containing groups into amino acids has attracted much attention from bioorganic and medicinal chemists because the resulting fluorinated amino acids have found wide application as potential enzyme inhibitors and antitumor (antibacterial) agents. Additionally, it is well known that replacement of naturally occurring amino acid(s) in some peptide chains with their fluorinated counterparts can significantly increase specific protein–ligand or protein–protein interactions, leading to increases in the proteolytic and thermal stabilities of peptide compounds and, as a result, promote their therapeutic properties. This microreview summarizes important advances in the synthesis of fluorinated amino acids since 2005. The contents are simply divided into three groups on the basis of amino acid types: fluorinated α-amino acids (F-αAAs), fluorinated β-amino acids (F-βAAs), and fluorinated cyclic amino acids (F-CAAs).

A facile method for preparation of fluorinated polyacrylate was developed. Novel multifunctional graft copolymer (GPF-1, 2, 3) containing short fluoroalkyl side chains and reactive groups were successfully prepared by grafting fluoroalcohols to polyacrylate. The obtained products were characterized by ¹H NMR, ¹⁹F NMR, FTIR, GPC, TGA, and XPS analyses. GPF-1, 2, 3 exhibited very low surface free energy (17.77–25.81 mJ/m²). Cotton fabric treated by GPF-1 had the highest water and oil repellency rating which was 100 and 6, respectively (AATCC test methods). The water and oil repellency rating was kept as 90 and 5, respectively, after 10 soaping cycles or 2 h uninterrupted soaping which indicated a very good washing durability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

A series of polyhedral oligomeric silsesquioxane (POSS) based hybrid copolymers poly(POSS-co-methyl methacrylate −co- 4-vinylbenzyl fluoroether carboxylate) (P(POSS-MMA-VBFC)) were prepared via radical polymerization and characterized by nuclear magnetic resonance, fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, gel permeation chromatography, X-ray powder diffraction, scanning electron microscopy and transmission electron microscopy. The thermal properties of these polymers (T_d > 250 °C) were improved by the introduction of POSS cage. The cotton fabrics coated with the polymers possessed excellent water and oil repellency. The water and salad oil contact angle could be achieved from 133° to 159° and from 127° to 141° respectively as the content of POSS in the polymer increased from 0 to 7.1 wt %. Moreover, the cotton fabric coated with the terpolymer was less flammable than the uncoated one. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A practical and stereoselective synthesis of the C(9)–C(24) subunit of (+)-discodermolide has been achieved. The strategy featured the construction of the key intermediate Z-trisubstituted vinyl iodide 12 from the dibromo-olefin 6 via an efficient modified Tanino-Miyashita's approach. The union of the two fragments was carried out through a Suzuki cross-coupling reaction.

A novel cross-linked copolymer containing hydrophobic perfluoropolyether and hydrophilic oligo(ethylene glycol) units was synthesized and characterized. The anti-biofouling properties of the fluoropolymer were evaluated by laboratory assays using the fouling diatom Nitzschia and bacteria Staphylococcus aureus and Escherichia coli. The results from the preliminary study showed that this fluorinated copolymer has promising anti-biofouling performance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Indium-mediated gem-difluoroallylation of aldehyde-derived N-acylhydrazones 1a–1q and 4a–4g with 3-bromo-3,3-difluoropropene 2 afforded α,α-difluorohomoallylic hydrazides 3a–3q and 5a–5g in high yields, respectively. Functional groups such as nitro, phenolic hydroxyl, benzyloxy and even C=C bonds of α,β-unsaturated aldehydes were compatible under this mild and operationally simple gem-difluoroallylic reaction condition. By means of substitution of Zn powder for indium, gem-difluoroallylation of ketone-derived N-acylhydrazones 6a–6d also provided the corresponding α,α-difluorohomoallylic hydrazides 7a–7d in medium yields. The N–N bond cleavage of the hydrazide 3a proceeded smoothly to give the corresponding primary gem-difluorohomoallylic amine 8, which could be converted to gem-difluoro-δ-substituted α,β-unsaturated lactam 11 via acryloylation followed by ring closing metathesis (RCM) reaction.