Abstract:Although the desulfurization of thiols is a topic of great importance and has received significant attention, most efforts have focused on the hydrodesulfurization of thiols. In this work, we describe the desulfurization of thiols for nucleophilic substitution. This process occurs rapidly, promoted by the Ph₃P/ICH₂CH₂I system, and can be extended to a wide range of nucleophiles. Notably, free amines can be employed as nucleophiles to synthesize various secondary and tertiary amines. This method tolerates a wide array of functional groups, including hydroxyl groups in amination reactions. Benzyl thiols are particularly reactive and can be completely converted at room temperature within 15 min. Although alkyl thiols show lower reactivity, they can also be converted smoothly at a reaction temperature of 70 °C overnight.

_{Abstract: Efforts to develop alternatives to triflic anhydride (Tf2O) as a trifluoromethylation reagent continue due to its limitations, including volatility, corrosiveness, and moisture sensitivity. Described herein is the use of a trifluoromethylsulfonylpyridinium salt (TFSP), easily obtained by a one-step reaction of Tf2O with 4-dimethylaminopyridine, as a reagent for the trifluoromethylative difunctionalization of alkenes by photoredox catalysis. DMSO and CH3CN are suitable solvents for achieving keto- and amino-trifluoromethylation of alkenes, respectively, with good functional group tolerance.}

Abstract: With the rapidly increasing prevalence of metabolic diseases such as type 2 diabetes mellitus (T2DM), neuronal complications associated with these diseases have resulted in significant burdens on healthcare systems. Meanwhile, effective therapies have remained insufficient. A novel fatty acid called S-9-PAHSA has been reported to provide metabolic benefits in T2DM by regulating glucose metabolism. However, whether S-9-PAHSA has a neuroprotective effect in mouse models of T2DM remains unclear.

Abstract: Ph₃P⁺CF₂CO₂^– (PDFA), a reagent that was developed by us recently, has found widespread applications in the synthesis of fluorinated molecules. Its great synthetic potential stimulates us to develop an effective synthetic route on a kilogram scale, which is described in this work. The used reagents are all cheap and easily available. We also demonstrate that the aldehyde group is significantly more reactive than the double bond group toward PDFA even though both of these two groups are very reactive toward PDFA.

Abstract: Difluorocarbene has found widespread applications in the synthesis of fluorine-containing molecules. We have previously found that difluorocarbene can react with elemental sulfur to produce thiocarbonyl fluoride, which is of great value for the new discoveries of difluorocarbene chemistry and the investigations of synthetic utilities of thiocarbonyl fluoride. We have developed the transformation of difluorocarbene into thiocarbonyl fluoride as a synthetic tool to achieve trifluoromethylthiolation of terminal alkynes and alkyl halides. In continuation of our research interest in this chemistry, herein we further apply the difluorocarbene transformation to the trifluoromethylthiolation of aryl and alkenyl iodides. Trifluoromethylthiolation is an active research area in organofluorine chemistry, and the commonly used trifluoromethylthiolation methods usually require the use of expensive CF₃S-containing reagents. In contrast, in our protocol the CF₃S group is generated in situ from difluorocarbene, elemental sulfur and a fluoride anion, all of which are cheap and easily available reagents. The general experimental procedure is shown as follows. Into a 5 mL sealed tube were added 4-phenyl phenyl iodide (1a, 56.0 mg, 0.2 mmol), S (57.8 mg, 1.8 mmol), Ph₃P⁺CF₂CO₂^– (PDFA) (213.8 mg, 0.6 mmol), AgF (0.5 mmol, 63.4 mg), ligand L1 (0.6 mmol, 158.9 mg), CuI (76.2 mg, 0.4 mmol), and dioxane (1.0 mL) under a N2 atmosphere. The reaction mixture was stirred at 110 ℃ for 8 h. After the reaction system was cooled to room temperature, Et₃N (0.5 mL) was added to remove the excess elemental sulfur by a redox reaction (the final product would be contaminated by elemental sulfur if elemental sulfur was not removed). The mixture was diluted with 10 mL of saturated brine, and then the product was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated to 1 mL. The residue was subjected to flash column chromatography to afford the pure product.

Abstract: Difluorocarbene has served as a versatile intermediate for the incorporation of fluorinated groups into organic molecules. Extensive studies have shown that difluorocarbene can act as a CF₂ source and a nonfluorinated C1 source. However, the use of difluorocarbene as a C–F source remains a challenging task. Herein we disclose that difluorocarbene can function as a C–F source for the cyclization of 2-aminobenzenethiols, allowing for the construction of fluorinated benzothiazoles, which may provide new possibilities for drug developments due to the magic effects of the fluorine element and the pharmacological properties of benzothiazoles.

Abstract: Fenofibrate is known as a lipid-lowering drug. Although previous studies have reported that fenofibrate exhibits potential antitumor activities, IC50 values of fenofibrate could be as high as 200 μM. Therefore, we investigated the antitumor activities of six synthesized fenofibrate derivatives. We discovered that one compound, SIOC-XJC-SF02, showed significant antiproliferative activity on human hepatocellular carcinoma (HCC) HCCLM3 cells and HepG2 cells (the IC50 values were 4.011 μM and 10.908 μM, respectively). We also found this compound could inhibit the migration of human HCC cells. Transmission electron microscope and flow cytometry assays demonstrated that this compound could induce apoptosis of human HCC cells. The potential binding sites of this compound acting on human HCC cells were identified by mass spectrometry-cellular thermal shift assay (MS-CETSA). Molecular docking, Western blot, and enzyme activity assay-validated binding sites in human HCC cells. The results showed that fumarate hydratase may be a potential binding site of this compound, exerting antitumor effects. A xenograft model in nude mice demonstrated the anti-liver cancer activity and the mechanism of action of this compound. These findings indicated that the antitumor effect of this compound may act via activating fumarate hydratase, and this compound may be a promising antitumor candidate for further investigation.

Abstract: Owing to the ubiquity of the hydroxyl group, reductive deoxygenation of alcohols has become an active research area. The classic Barton–McCombie reaction suffers from a tedious two-step procedure. New efficient methods have been developed, but they have some limitations, such as a narrow substrate scope and the use of moisture-sensitive Lewis acids. In this work, we describe the Ph₃P/ICH₂CH₂I-promoted reductive deoxygenation of alcohols with NaBH₄. The process is applicable to benzyl, allyl and propargyl alcohols, and also to primary and secondary alcohols, demonstrating a wide substrate scope and a good level of functional group tolerance. This protocol features convenient operation and low cost of all reagents.

Abstract: Difluorocarbene has served as a versatile intermediate in organic synthesis. The transformation of difluorocarbene into thiocarbonyl fluoride, which was discovered by us previously, can be developed as a synthetic toolfor the cyclization of vicinal X-H substituted amines to provide various five-membered heterocycles. However,aryl amines are required to be used and difluoromethylation of the N–H bond or a newly generated S-H bondcannot be suppressed. Herein we describe the use of thiocarbonyl fluoride generated in situ as a thiocarbonylsource for the cyclization of vicinal X-H substituted alkyl amines (X = N, O, S) to provide imidazolidine-2-thiones, oxazolidine-2-thiones and thiazolidine-2-thiones. The use of alkyl amines constructs different heterocycles with those obtained from aryl amines. The free N–H bond remains intact without beingdifluoromethylated.

Abstract: Due to its unique electronic properties, the difluoromethylene group (CF₂) has served as a valuable unity in the design of biologically active molecules. Since γ-lactones display a broad range of biological properties, α,α-difluoro-γ-lactones may exhibit unexpected biological activities, and thus their synthesis has received increasing attention. Traditional synthetic methods suffer from tedious multi- step processes, and very few effective methods have been reported recently. Herein, we describe the difunctionalization of alkenes with BrCF₂CO₂K under photoredox catalysis with the use of a boron-Lewis acid for the access to α,α-difluoro-γ-lactones. In this transformation, the alkene substrates and the used reagents, including BrCF₂CO₂K and the boron-Lewis acid, PhB(OH)₂ or BF₃·THF, are cheap and widely available. High efficiency and atom economy may make this protocol attractive.

Abstract: Described here is the R₃P/ICH₂CH₂I-promoted dehydroxylative sulfonylation of alcohols with a variety of sulfinates. In contrast to previous dehydroxylative sulfonylation methods, which are usually limited to active alcohols, such as benzyl, allyl, and propargyl alcohols, our protocol can be extended to both active and inactive alcohols (alkyl alcohols). Various sulfonyl groups can be incorporated, such as CF₃SO₂ and HCF₂SO₂, which are fluorinated groups of interest in pharmaceutical chemistry and the installation of which has received increasing attention. Notably, all reagents are cheap and widely available, and moderate to high yields were obtained within 15 min of reaction time.

Abstract: A Ph3P/ICH2CH2I-promoted dehydroxylative cyanation of alcohols avoids the use of transition metals or moisture-sensitive Lewis acids. This protocol features convenient operations, mild reaction conditions, and the use of cheap and widely available reagents.

Abstract: Described herein is the convenient synthesis of an efficient trifluoromethoxylation reagent, nC₄F₉SO₃CF₃, by using cheap and widely available reagents and without the need of any tedious column chromatography purification procedure.

Abstract: Depending on the nature of the attached functional moiety, the sulfonyl radical can either undergo an automatic SO₂ liberation or react directly as the thermodynamically favored sulfonyl radical. Taking advantage of this unique property, we envisioned that through rational reaction design, the in situ release and re-insertion of SO₂, i. e., the shuttle of SO₂, can be realized. Herein we report our recent progress in copper metallaphotoredox co-catalyzed trifluoromethyl-fluorosulfonylation of alkenes with TFSP as both the CF₃ and SO₂ source. Valuable functional groups are added across the double bonds. Besides, A wide array of synthetically useful moieties featuring distinct electronic patterns and various nitrogenous heterocycles are well tolerated by this strategy.

Abstract: Cyanex923 (a mixture of four trialkyl (hexyl and octyl) phosphine oxides) has been extensively employed in the recovery of cerium (Ce(IV)) and fluorine (F), as well as the separation over thorium (Th(IV)) from bastnaesite. However, rigorous production conditions and involvement of highly toxic raw materials (PH₃) have been critical problems to be solved during the synthesis of Cyanex923. Meanwhile, its extraction performance remains to be improved. Therefore, we attempted to adjust the feed ratio to increase the proportion of short carbon chain components, successfully synthesized a novel extractant (P113, a mixture of four trialkyl (hexyl and octyl) phosphine oxides) with contents of each component different from Cyanex923 using an environmentally benign method. The comparison with Cyanex923 revealed obvious improvement of P113 in terms of extraction efficiency, selectivity and saturation capacity. The extraction efficiency and saturation capacity of Ce(IV) were increased by 10% and 10 g L-1, respectively. Separation factor of Ce(IV)/Th(IV) was increased from 16 to 27 at 2 mol L-1 H₂SO₄. Furthermore, P113 presented excellent regenerability. The superiority of P113 was theoretically explored using the density functional theory (DFT) and polarizable continuum model (PCM), and the results indicated that THPO (trihexyl phosphine oxide) had lower extraction phase transfer energy than TOPO (trioctyl phosphine oxide) from aqueous phase to organic phase. The comprehensive evaluation of P113 demonstrated the feasibility employed in the recovery of Ce(IV)-F and the separation of Th(IV) from bastnaesite, which advanced industrial application of the novel extractant, and held significant value for the utilization of resources and environmental protection.

Abstract: Herein, we describe the design and synthesis of a difluoromethylsulfonyl imidazolium salt, which can act as a radical difluoromethylation reagent to achieve the challenging amino- and oxy-difluoromethylation of alkenes. Notably, the three steps for the synthesis of the imidazolium salt do not require any tedious distillation or column chromatography purification process, and the amino- and oxy-difluoromethylation paths are simply determined by the selection of reaction solvents.

Abstract: The trifluoromethylsulfonyl pyridinium salt (TFSP) was used as a CF₃S source for the trifluoromethylthiolation of indole derivatives. It is proposed that TFSP is reduced in the presence of diethyl phosphite and NaCl. The protocol features a facile access to the CF₃S source, and high efficiency and transition-metal free conditions for trifluoromethylthiolation.

Abstract: A successful Cu-catalyzed addition of both Cl and SO₂OCF₂H groups into alkenes allows us to discover the unusual reactivity of the SO₂OCF₂H group. As opposed to common sulfonic esters (RSO₂-O-R′), in which the R′ group is highly electrophilic, the SO₂ moiety demonstrates higher electrophilicity in RSO₂–OCF₂H. The unexpected reactivity is further developed not only as a synthetic tool for well-functionalized alkenyl sulfonyl fluorides but also for the first ¹⁸F labeling of alkenyl sulfonyl fluorides.

Abstract: Tetraphenylporphyriyne (Pyne1), a novel porphyrin analogue with a C≡C bond incorporated into an 18-π-conjugated system, has been created via cleavage of the N-confused pyrrolic ring in Ag(III) N-confused tetraphenylporphyrin. The structure of Pyne1 was confirmed by X-ray crystallography and ¹H NMR, IR, and UV–vis spectroscopy. The mechanism of cleavage of the N-confused pyrrolic ring was investigated by theoretical calculations. The successful synthesis of other Pynes indicated the generality of this protocol.

Abstract: The fluorination of alkenes with electrophilic N−F type reagents usually occurs through a Markovnikov-type addition, and the anti-Markovnikov-type addition may require the use of a transition metal catalyst or an expensive catalyst. Herein we describe a convenient anti-Markovnikov iodofluorination of alkenes with Selectfluor/nBu₄NI. A wide substrate scope and good functional group tolerance were observed. The process allows for the construction of various C−F bonds, especially tertiary C−F bonds. The remarkable features make this protocol attractive, including convenient operations, simple reaction conditions, and the installation of an iodine atom which provides possibilities for further transformations.

Abstract: A protocol for visible light mediated C–H trifluoromethylation of unactivated (hetero)arenes under blue LED irradiation has been developed. The reaction enables the rapid construction of a range of CF₃-containing (hetero)arenes in moderate to high yields from the readily accessible trifluoromethylsulfonyl-pyridinium salt (TFSP). This protocol is also suitable for nitrogen-containing aromatic heterocycles, which are potentially useful in medicinal chemistry.

Abstract: Heptafluoroisopropylthio group (-SCF(CF₃)₂) has bioactivities in insecticidal molecules, but the protocol for direct introduction of -SCF(CF₃)₂ is under-explored. Described here is a protocol on heptafluoroisopropylthiolation of benzyl halides with a hexafluoropropylene (HFP)/CsF/S₈ system. The reaction enables the rapid construction of a range of (CF₃)₂CFS-containing compounds from readily available materials. This protocol may find application in the synthesis of (CF₃)₂CFS-containing biologically active molecules.

Abstract: The study of transition-metal difluorocarbene complex has long been a subject of active investigation, but the transition-metal-catalyzed transfer of difluorocarbene remains a significant challenge. The Pd-catalyzed transfer of difluorocarbene is described to realize the coupling reaction of boronic acids with difluorocarbene to give (difluoromethyl)arenes and -olefins. Mechanistic investigations reveal that the Pd═CF₂ complex is an important intermediate for this transformation. This complex is prone to trimerization without the presence of starting materials.

Abstract: A convenient method for deoxyfluorination of aromatic and aliphatic carboxylic acids with CF₃SO₂OCF₃ in the presence of a suitable base at room temperature has been developed. The reaction allows a straightforward access to a variety of acyl fluorides and proves that CF₃SO₂OCF₃ is an effective deoxyfluorination reagent for carboxylic acids. The method features simplicity, expeditiousness, high efficiency, ease of handling, good functional group tolerance, a wide range of substrates, excellent yields of products, compatibility of many amine initiators, use of environmentally friendly reagents, and effortless removal of byproducts. This reaction represents the first utilization of trifluoromethyl trifluoromethanesulfonate as a fluorination reagent.

Abstract: A large number of fluorination methods have been developed, but the construction of a tertiary C−F bond remains challenging. Herein, we describe an efficient dehydroxylative fluorination of tertiary alcohols with Selectfluor via the activation of a hydroxyl group by a Ph₂PCH₂CH₂PPh₂/ ICH₂CH₂I system. Although the reagents appear to be not compatible (Selectfluor with the phosphine and I− generated in situ), the reactions occur rapidly to give the desired products in moderate to high yields. This work may present a new discovery in fluorination of alcohols since the reported methods are mainly limited to primary and secondary alcohols.

Abstract:  Owing to the special effects of the fluorine element, including high electronegativity and small atomic radius, the incorporation of a fluorinated group into organic molecules may modify their physical, chemical, and biological properties. Fluorine containing compounds have found widespread application in a variety of areas, and thus, the development of efficient reagents and methods for the incorporation of fluorinated groups has become a subject of significant interest. Described in this Account are our recent discoveries in the chemistry of fluorinated ylides/carbenes and related intermediates generated from phosphonium/sulfonium salts. Initially, we obtained the (triphenylphosphonio) difluoroacetate, Ph₃P⁺CF₂CO₂^- (PDFA), which was proposed as a reactive intermediate but had never been successfully synthesized. PDFA, shelf-stable and easy to prepare, is not only a mild ylide (Ph₃P⁺CF₂^-) reagent, but also an efficient difluorocarbene source. It can directly generate difluorocarbene, via the first generation of ylide Ph₃P⁺CF₂^-, simply under warming conditions without the need for any additive. Interestingly, difluorocarbene chemistry was then discovered by using PDFA as a reagent. Difluorocarbene can be oxidized to CF₂=O, can react with elemental sulfur to afford CF₂=S, and can be trapped by NaNH₂ or NH₃ to give CN^-. The development of these processes into synthetic tools allowed us to achieve various reactions, including the challenging 18F trifluoromethylthiolation and cyanodifluoromethylation. It was found that a substituent on the cation of a phosphonium salt can be directly transferred as a nucleophile despite the cation’s high electrophilicity. This transfer process is like an “umpolung” of the cation, which may provide more opportunities for the synthetic utilities of phosphonium salts. The investigation of this transfer process led us to find that iodophosphonium salts, active intermediates which can be easily generated, may efficiently promote deoxygenative functionalizations of aldehydes and alcohols. Dehydroxylative substitution of alcohols by this protocol permits the use of unprotected amines with higher pΚa values as nucleophiles, which is an attractive feature compared with the Mitsunobu reaction. On the basis of the ylide-tocarbene process (Ph₃P⁺CF₂^- → :CF₂), we further developed sulfonium salts as precursors of fluorinated ylides and fluorinated methyl carbenes. In particular, the studies on difluoromethylcarbene, remaining largely unexplored, may deserve more attention. The discoveries may find utility in the synthesis of biologically active fluorine-containing molecules.

Abstract:  A large number of trifluoromethylthiolation methods have been developed, but a trifluoromethylthiolation reagent usually has to be used in these methods. Herein we describe a difluorocarbene-based trifluoromethylthiolation of terminal alkynes to construct a Csp-SCF₃ bond catalysed by a copper complex. Ph₃P⁺CF₂CO₂^-/S₈/F^- was used as a reagent system to form the CF₃S- anion, and the sequential formation of CF₂=S, F-CF₂S and C-SCF₃ bonds was achieved in a one-step process.

Abstract: We report herein a general and practical coppercatalyzed fluorosulfonylation reaction of a wide range of abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a convenient sulfonyl source in combination with KHF₂ as an ideal fluorine source and without the need for additional oxidants. Interestingly, the electronic character of the arene ring in the starting arenediazonium salts has a significant impact on the reaction mechanistic pathway.

Abstract: In order to provide feasible methods for the extraction of valuable metals from spent batteries or low-grade primary ores, the extraction behavior of some representative acidic phosphoruscontaining compounds (APCC) as extractants is evaluated from the perspective of experimental and theoretical investigations in this work. Aqueous solutions containing five metal ions, Ca(II), Co(II), Mg(II), Mn(II), and Ni(II), were made to simulate leaching liquids, and the extraction of these metals were investigated. A simplified calculated model was used to evaluate the interaction between each extractant and metal ions. The calculation results agree well with the experimental tests in trend. This work not only provides potential extractants for the extraction of valuable metals from spent batteries or low-grade primary ores, but also demonstrates the practicability of the simplified calculation model

Abstract: For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.

Abstract: CF₃S,CF₃ and HCF₂ groups have been identified as valuable functionalities for drug development. Despite significant accomplishments in the trifluoromethylthiolation,trifluoromethylation and difluoromethylation reactions,directly converting common functional groups into CF₃S,CF₃ or HCF₂ groups are still highly desirable. Described here is the dehydroxylative trifluoromethylthiolation,trifluoromethylation and difluoromethylation of alcohols promoted by a R₃P/ICH₂CH₂I system. All of these dehydroxylative reactions were achieved under mild conditions via the activation of the hydroxyl group by the R₃P/ICH₂CH₂I system. A wide substrate scope and good functional group tolerance were observed.

Abstract: As a versatile intermediate, diflfluorocarbene is an electron-defificient transient species, meaning that its oxidation would be challenging. Herein we show that the oxidation of diflfluorocarbene could occur smoothly to generate carbonyl flfluoride. The oxidation process is confifirmed by successful triflfluoromethoxylation, 18O-triflfluoromethoxylation, the observation of AgOCF₃ species, and DFT calculations.

Abstract:Described here is the radical-mediated hydrodifluoromethylation of alkenes that occurs under transition-metal-free conditions by using the phosphonium salt [Ph₃P⁺CF₂H]Br^- irradiated with a 26 W household compact fluorescent light. The reaction lends itself to a convenient protocol for the installation of a C-CF₂H bond while maintaining good functional group tolerance.

Abstract: Photocatalyzed cyanodifluoromethylation of alkenes with a Ph₃P⁺CF₂CO₂^- /NaNH₂ (or NH₃) system is described. Ph₃P⁺CF₂CO₂^- acted as both the HCF₂ source and CN carbon source, and the cyanide anion was generated in situ under mild conditions, avoiding the use of toxic cyanation reagents.

Abstract: As trifluoromethylthiolation has received increasing attention recently, many CF₃S-reagents and trifluoromethylthiolation methods have been developed. Herein we describe trifluoromethylthiolation of alkyl halides by using Ph₃P⁺CF₂CO₂⁻ as a fluoride and difluorocarbene source. Difluorocarbene is a versatile intermediate, but its side reactions are usually ignored and the by-products would therefore be discarded. In this work, a side reaction of difluorocarbene, the generation of a fluoride anion from difluorocarbene, was developed into a synthetic tool. Although the trifluoromethylthiolation reaction involved multi-sequential steps, the cleavage of C–F bond, the formation of CF₂=S bond, F-C(S)F₂ bond, and C-SCF₃ bond, the conversion proceeded fast and was completed within 10 min.

Abstract: Cu-Promoted difluorocarbene-derived trifluoromethylselenolation of benzyl halides with the Ph₃P⁺ CF₂CO₂/Se/F system is described. Three new carbon–heteroatom bonds, a Se–CF₂ bond, SeCF₂–F bond, and C–SeCF₃ bond, were sequentially formed in the reaction. This work represents the first trifluoromethylselenolation protocol involving an external fluoride for the generation of the key intermediate, CF₃Se anion.

Abstract: Wittig gem-difluoroolefination of aldehydes with difluoromethyl phosphonium salt (Ph₃P^＋CF₂H•Br^－) by using zinc oxide as a base is described. Although the proton in the CF₂H group is acidic and a base could easily lead to its deprotonation to form ylide ( Ph₃ P CF₂ ^-), the attack of the base at the positive phosphorus atom may also take place to produce a nucleophilic [ HCF₂^－ ] equivalent, and then nucleophilic difluoromethylation instead of Wittig reaction would occur. The use of ZnO as the base favored the Wittig reaction and the nucleophilic difluoromethylation was not observed. Furthermore, the excessive ZnO and ZnII salts produced from ZnO could be easily removed by filtration, which may be convenient for the purification process.

Abstract ：Ph₃P/I–-promoted dichlorination and dibromination of epoxides by using XCH₂CH₂X (X = Cl or Br) as the halogen source and reaction solvent is described. All reagents are widely available and easy to handle, and mild conditions and operational simplicity make this protocol attractive.

Abstract: Ag-mediated triflfluoromethylthiolation of inert Csp³−H bond with CF₃SOCl is described. Widely available reagents and operational simplicity make this protocol attractive.

Abstract: Although CF₃SO₂Cl is an efficient chlorotrifluoromethylation reagent, an expensive transition metal complex usually has to be used. We found that CuCl₂-catalyzed chlorotrifluoromethylation of alkenes with CF₃SO₂Cl occurred smoothly under mild conditions. A wide substrate scope and good functional group compatibility were observed.

Abstract: The preparation of highly pure KF-ZrF₄ (FKZr) molten salt, a potential secondary coolant in molten salt reactors, was realized simply by heating a mixture of (NH₄)₂ZrF₆ and KF. X-ray diffraction analysis indicated that the FKZr molten salt was mainly composed of KZrF₅ and K₂ZrF₆. The melting point of the prepared FKZr molten salt was 420–422 °C under these conditions. The contents of all metal impurities were lower than 20 ppm, and the content of oxygen was lower than 400 ppm. This one-step protocol avoids the need for a tedious procedure to prepare ZrF4 and for an additional purification process to remove oxide impurities, and is therefore a convenient, efficient and economic preparation method for high-purity FKZr molten salt.

Abstract: Fluoride molten salt has many advantages，such as high temperature stability，high thermal conductivity，large heat capacity，wide electrochemical window，low saturated vapor pressure and small neutron absorption cross section. It is an important functional material which has found widespread applications. The typical preparation and purification methods of fluoride molten salt，including vacuum dehydration，fluorination using ammonium fluoride，H₂-HF purification，electrochemical purification and reduction with metals，are introduced in detail. The mechanism and technical characteristics are analyzed for the different methods that are used to remove impure ions in molten salt. At the same time，the applications and progress of fluoride molten salts in nuclear energy，metallurgy， functional materials preparation，advanced energy storage medium，surface treatment technology， electronic chemicals，fine chemicals and molten salt battery materials are reviewed. The fluoride molten salts are mainly used as the nuclear reactor coolant，molten salt electrolyte，high temperature energy storage material and reaction medium. The existing problems in this area are also discussed. It is important to study and clarify the preparation and purification mechanism of fluoride molten salt，toexplore the existence form and impurity migration nature in the process of fluoride purification，and to develop a new method for the purification of the molten salt to reduce its corrosion and cost.

SUMMARY: The CF₃O functional group is a unique flfluorinated group that has received a great deal of attention in medicinal chemistry and agrochemistry. However, triflfluoromethoxylation of substrates remains a challenging task. Herein we describe the dehydroxytriflfluoromethoxylation of alcohols promoted by a R₃P/ICH₂CH₂I (R₃P = Ph₃P or Ph₂PCH=CH₂) system in DMF. P-I halogen bonding drives the reaction of R₃P with ICH₂CH₂I in DMF to generate iodophosphonium salt (R₃P+I I) and a Vilsmeier-Haack-type intermediate, both of which could effectively activate alcohols, thus enabling a fast (15 min) triflfluor omethoxylation reaction. A wide substrate scope and a high level of functional group tolerance were observed.

Abstract:Difluoromethylation of N-arylsulfonyl hydrazones with difluorocarbene generated from difluoromethylene phosphobetaine (Ph₃P⁺CF₂CO₂^-) to give various difluoromethyl aryl sulfones is described.

Abstract:Outstanding accomplishments have been achieved in the chemistry of difluorocarbene, but transition‐ metal‐catalyzed transfer of difluorocarbene for coupling remains a challenging task. Herein, we describe a Pd‐catalyzed coupling of difluorocarbene with two aryl carbon centers to give difluoromethylenation products, which cannot be obtained by any previous difluorocarbene‐transformation method.

Abstract:Phosphonium salt ([Ph₃P+CF₂H] Br^–, DFPB) was found to be an efficient nucleophilic difluoromethylation reagent. Although DFPB is known as a phosphonium ylide precursor, its reaction with carbonyl compounds under traditional “Wittig reaction conditions” did not give the expected Wittig difluoroolefinated products, but afforded the nucleophilic difluoromethylation products, α-CF₂H alcohols. Mechanistic investigation reveals that the unexpected transformation proceeded via the direct transfer of the CF₂H group, which resulted from the high P–O affinity.

Abstract:In this work, the effect of the substituent at the α or β position in dialkylphosphinic acids on the extraction of trivalent lanthanide ions was investigated using experimental and theoretical methods. Five dialkylphosphinic acids were synthesized. Their extractions of seven trivalent lanthanide ions, La/Pr, Nd/Dy, and Ho/Yb/Lu, which represent light, middle, and heavy rare-earth metals, were explored. A simplified coordination model was built to explore the bonding between the extractants and lanthanide ions. The results obtained using this model generally explained the experimental results. The model could therefore be used to study the effects of the α and β substituents of extractants on their extraction properties. The theoretical and experimental results indicate that the significance of a β substituent in the dialkylphosphinic acid on extraction was greater than that of an α substituent.

Abstract:The trifluoromethylcarbene (:CHCF₃) was found to be conveniently generated from (2,2,2-trifluoroethyl)diphenyl-sulfonium triflate (Ph₂S⁺CH₂CF₃^–OTf), which was successfully applied in Fe-catalyzed cyclopropanation of olefins, giving the corresponding trifluoromethylated cyclopropanes in high yields.

Abstract:The differences of thermodynamics energies from the pure phase to a solution were used to predict the solubility properties of acidic phosphorus–containing rare-earth extractants. Four solvents, namely tributylphosphate, n-dodecane, toluene, and n-octanol were used. The thermodynamic cycle of the implicit solvation model and the structure model with short carbon chains were used. The relationship obtained by simulation of the solubility properties and extractant structures agreed qualitatively with reported experimental results. These results provide guidance for the design of new efficient extractants.

Abstract:DBU‐promoted trifluoromethylation of aryl iodides with difluoromethyltriphenylphosphonium bromide (DFPB) in the presence of copper source is described. In this transformation, DBU not only acts as base to deprotonate the difluoromethyl group in DFPB to generate difluoromethylene phosphonium ylide Ph₃P⁺CF₂⁻, but also converts the difluorocarbene generated from ylide Ph₃P⁺CF₂⁻ into trifluoromethyl anion, finally resulting in the trifluoromethylation of aryl iodides. The reactions proceeded smoothly to afford expected products in moderate to good yields.

Abstract:A new method has been developed for the Cu-catalyzed C–H trifluoromethylation of 3-arylprop-1-ynes for the selective construction of allenic Csp₂–CF₃ and propargyl Csp₃–CF₃ bonds. The selective formation of allenic Csp₂–CF₃ and propargyl Csp₃–CF₃ bonds can be controlled by modifying the reaction conditions.

Abstract:Organic phosphonium salts have served as important intermediates in synthetic chemistry. But the use of a substituent on the positive phosphorus as a nucleophile to construct C–C bond remains a significant challenge. Here we report an efficient transition-metal-free protocol for the direct nucleophilic arylation of carbonyls and imines with tetraarylphosphonium salts in the presence of caesium carbonate. The aryl nucleophile generated from phosphonium salt shows low basicity and good nucleophilicity, as evidenced by the successful conversion of enolizable aldehydes and ketones. The reaction is not particularly sensitive to water, shows wide substrate scope, and is compatible with a variety of functional groups including cyano and ester groups. Compared with the arylmetallic reagents that are usually moisture sensitive, the phosphonium salts are shelf-stable and can be easily handled.

Abstract:The O-difluoromethylation of 1,3-diones with S-difluoromethyl sulfonium salt is described. The sulfonium salt was previously believed to be a direct difluoromethylation reagent, but our mechanistic investigation reveals that the O-difluoromethylation reaction proceeds not only via the direct transfer of the CF₂H group, but also via a difluorocarbene process. This work represents the first protocol for mild O-difluoromethylation of acyclic 1,3-diones.

Abstract:(NH₄)₂BeF₄ was synthesized and purified by recrystallization to remove sulfate ions before being used as the main raw material to prepare Li₂BeF₄ molten salt. (NH₄)₂BeF₄ was heated and melted with LiF at high temperature to produce Li₂BeF₄ molten salt without separate BeF₂ preparation by pyrolysis. The obtained salt has a melting point of 458–460°C and an oxygen content below 500ppm. The main impure metal ion and anion concentrations are less than 10ppm and 80ppm, respectively. This is a convenient, efficient and economical preparative method for high-purity Li₂BeF₄ molten salt

Abstract:Dialkylphosphinic acids were synthesised by a microwave-assisted method with high yields and wide substrate applicability. A structure–reactivity study indicates that an increase in steric hindrance in the b position led to a decrease of extraction ratio and heavy rare earth element separation activity. A computational study was also conducted to understand the steric effect.

Abstract: Cross-coupling between difluorocarbene and carbene-derived intermediates generated from diazocompounds was developed to give gem-difluoroolefins, which constitutes a fast practical pathway to achieve hindered gemdifluoroolefins. The cross-coupling between difluorocarbene and aryl diazoacetates proceeded smoothly in the presence of a copper source, whereas its coupling with diaryl diazomethanes occurred well under metal-free conditions. A mechanism involving a copper−difluorocarbene complex was proposed.

Abstract: Csingle bondF 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 Csingle bondF bond cleavage examples and further transformation of compounds bearing with an aliphatic fluoride, difluoromethylene group or trifluoromethyl groups. The methods to activate a Csingle bondF 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.

Abstract: A new approach for the synthesis of gem-difluorostyrenes from benzyl bromide is described. Quaternization of triphenylphosphine with benzyl bromide to give phosphonium salts, deprotonation of the corresponding phosphonium salts to produce phosphonium ylide, and the subsequent olefination of phosphonium ylide with difluorocarbene generated from difluoromethylene phosphobetaine (Ph₃P⁺CF₂CO₂⁻) by decarboxylation can occur smoothly in one-pot, furnishing the final gem-difluorostyrenes in good yields.

Abstract: As both trifluoromethylthio (CF₃S) and trifluoromethoxy (CF₃O) moieties have proved to be valuable functionalities in pharmaceutical chemistry, trifluoromethylthiolation and trifluoromethoxylation have received a great deal of attention. For the trifluoromethylthiolation reaction, a variety of efficient methods have been developed. Among these methods, C-H trifluoromethylthiolation avoids the need to prefunctionalize substrates, meaning that this straightforward protocol is quite attractive and promising. The first section of this review summarizes recent advances in this field, including Csp³-H, Csp²-H and Csp-H trifluoromethylthiolation and the asymmetric Csp³-H trifluoromethylthiolation reactions. Trifluoromethoxylation with safe trifluoromethoxylation reagents remains a significant challenge. The second section of this review summarizes the recent progress in trifluoromethoxylation reaction.

Abstract: The visible-light-induced photoredox difunctionalization reactions of styrenes with 1,1,1-trifluoro-2-iodoethane under an oxygen atmosphere in the presence of water give γ-trifluoromethyl alcohols. In this radical reaction, the oxygen atom in the product originates from molecular oxygen, and water is shown to be important to promote the reaction.

Abstract: (2,2,2-Trifluoroethyl)diphenylsulfonium triflate was found to be an efficient ylide reagent for the Johnson–Corey–Chaykovsky reaction to afford trifluoromethyl epoxides, cyclopropanes and aziridines. Interestingly, excellent but different diastereoselectivity was observed for these transformations. Both trifluoromethyl epoxides and cyclopropanes were obtained with trans-selectivity, whereas aziridines were obtained with cis-selectivity.

Abstract: A stereoselective N-iminium ion cyclization with allylsilane to construct vicinal quaternary–tertiary carbon centers was developed for the concise synthesis of (±)-cephalotaxine. The current strategy features a TiCl₄-promoted cyclization and ring-closure metathesis to furnish the spiro-ring system. The stereochemical outcome in the N-acyliminium ion cyclization was rationalized by the stereoelectronic effect of the Z- or E-allylsilane. Two diastereomers arising from the cyclization were merged into the formal synthesis of (±)-cephalotaxine.

Abstract: Difluoromethylation of the activated X–H bond (X = N, O and S) and aliphatic thiols, and gem-difluorocyclopropenation of alkynes with difluorocarbene generated in situ from difluoromethylene phosphobetaine (Ph₃P⁺CF₂CO₂⁻) by decarboxylation occurred smoothly without the presence of any base or other additives.

Abstract: A practical and efficient method for the direct trifluoromethylthiolation of unactivated C(sp³)H bonds by AgSCF₃/K₂S₂O₈ under mild conditions is described. The reaction has a good functional-group tolerance and good selectivity. Initial mechanistic investigations indicate that the reaction may involve a radical process in which K₂S₂O₈ plays key roles in both the activation of the C(sp³)H bond and the oxidation of AgSCF₃.

Abstract: Difluorocarbene derived from various carbene precursors could be effectively decomposed by 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). This decomposition process was successfully applied in the subsequent trifluoromethylation of a variety of (hetero)aryl iodides without the addition of an external fluoride ion. Mechanistic investigation revealed the detailed difluorocarbene conversion process in which the decomposed difluorocarbene is finally transformed into a fluoride ion and carbon monoxide.

Abstract: As a well-developed high-temperature heat carrier, FLiNaK molten salt is cheap and thermodynamically stable. It can be used as the second coolant in high-temperature molten salt reactor and solar heat transfer medium. The presence of oxygen greatly influenced the function of the molten salt reactor such as reducing the solubility of nuclear fuel, the precipitation of uranium oxide which would further lead to local overheating of the fuel circuit. However, there are still no general methods for the analysis of trace oxygen in the molten salt now. Based on the application of oxygen analyzer in the determination of trace oxygen in steel industry, we developed a practical method for the measurement of trace oxygen in FLiNaK molten salt. Optimal test conditions including suitable package container and the cracking power 2800 W were established. The relative standard deviations of oxygen were 3.1% and the recoveries were 85%~101%.

Abstract: Tests on rem oval of sulfate radical contained in beryllium hydroxide were conducted with several different methods ，including washing，barium chloride precipitation and a combined method of hydrolysis by sodium hydroxide and precipitation．Results indicated that washing method had the worst effect，resulting in only 50％ sulfate radical removed．And the method of barium chloride precipitation brought the content of sulfate radical in beryllium hydroxide remarkably reduced to less than 0.3％，which，however，was put at a disadvantage by its high cost and possibly accompanied pollution problem．By comparison ，the third method of hydrolysis by sodium hydroxide followed by precipitation could reduce the content of sulfate radical from 6.77％ to less than 0.020％，with removal rate up to 99.7％ ．Furthermore ，this method being characterized by low cost and free of secondary pollution，may be of reference for preparation of beryllium hydroxide of nuclear grade purity．

Abstract: AuI/CuI-co-catalyzed tandem 1,3-acyloxy migration/trifluoromethylation reaction of propargyl esters to give α-trifluoromethyl enones in moderate yields and with excellent stereoselectivity is described. It is proposed that the reaction proceeds through the 1,3-acyloxy migration of the propargyl esters catalyzed by AuI to produce an allenic intermediate, followed by its trifluoromethylation to give the final product.

Abstract: Copper-catalyzed tandem trifluoromethylation/cyclization of internal alkynes with Umemoto's reagent leads to 3-trifluoromethyl-1,2-dihydronaphthalene derivatives in moderate to good yields. The utility of this copper-catalyzed tandem reaction was demonstrated by oxidizing and reducing the trifluoromethylated product to give naphthalene and tetrahydronaphthalene, respectively, and the development of a short route to a trifluoromethylated analogue of Nafoxidine.

Abstract: The past decade has witnessed the significant advances of asymmetric organocatalytic fluorination, monofluoroalkylation, gem-difluoroalkylation, and trifluoromethylation. This digest summarizes the latest progress of these reactions. In the research area of asymmetric organocatalytic fluorination, a new catalysis concept, chiral anion phase-transfer catalysis strategy, has emerged and has proved to be highly efficient. Asymmetric organocatalytic monofluoroalkylation and gem-difluoroalkylation have been much less explored and the Lewis base/acid catalysis has been the most used strategy. Compared with electrophilic trifluoromethylation, nucleophilic trifluoromethylation has been intensively studied in the research field of asymmetric organocatalytic trifluoromethylation.

Abstract: Salting-out agents, such as NaCl, were often used in solvent extraction in order to adjust distribution ratio. However, the high-concentration salting-out agent and the low-concentration rare earth in extraction phase create extraordinary difficulties to the accurate measurement of the concentration of rare earths due to the serious spectrum interference of salting-out agent itself. The spectrophotometry and ICP-AES were employed as simple and effective methods for the measurement of rare earths. Nevertheless, both methods were easily affected by the salting-out agent in solvent extraction. The influence of NaCl on the spectrophotometry and ICP-AES measurements was investigated in detail. The experiments showed that the accurate measurement of the rare earth was realized through the combination of spectrophotometry and ICP-AES in the presence of NaCl. For the measurement of the light (La, Ce, Pr, Nd) and middle (Sm, Eu, Gd) rare earths, their concentration could be accurately measured by spectrophotometry when the concentration of NaCl was lower than 0.08 mol·L-1 without matrix-matched. The measured value was lower than the real concentration when the concentration of NaCl was higher than 0.08 mol·L-1 without matrix-matched. It was found that in the case of measurement of the heavy rare earths, matrix-matched condition was necessary for both spectrophotometry and ICP-AES methods. The optical method for the measurement of the light (La, Ce, Pr, Nd) and middle (Sm, Eu, Gd) rare earths is that the concentration of sample is diluted to less than 0.08 mol·L-1 and measured by spectrophotometry method. For the measurement of heavy rare earths, ICP-AES method is recommended under matrix-matched condition.

Abstract: A convenient and effective synthesis of various novel beta-perfluoroalkylated subporphyrins has been developed. beta-Trifluoromethylated subporphyrins were efficiently synthesized by the reaction of brominated subporphyrins with FSO₂CF₂CO₂Me/CuI [with or without Pd(dba)(2)]. Potentially valuable beta-perfluoroalkylated, beta-monotetrafluorobenzo, and beta-monotrifluorobenzo subporphyrins were successfully obtained by a modified sulfinatodehalogenation reaction. Photophysical and electrochemical studies on several typical perfluoroalkylated subporphyrins demonstrated that beta-hexakis-trifluoromethylated subporphyrins show an obviously red-shifted UV/Vis absorption band that arises from macrocycle nonplanar distortion induced by trifluoromethyl groups, but this distortion is not so severe as that of the corresponding beta-octakis(trifluoromethyl)meso-tetraphenylporphyrin. This was supported by their redox potential data. In addition, beta-monotrifluorobenzo subporphyrin exhibits a special fluorescence spectrum of vibronic structure.

Abstract: Oxidative coupling of benzylamines to imines by molecular oxygen is efficiently realized in the presence of very low catalyst loadings of Co(II) β-tetrakis(trifluoromethyl)-meso-tetraphenylporphyrin. Due to the effect of four β-CF₃ groups, the catalyst shows good selectivity and very high turnover number. The reaction is easily scaled up and may provide a convenient way to prepare many imines in large scale. 

Abstract: A mild method of converting arylamines into perfluoroalkylated arenes is described. Relatively stable RFCu(CH₃CN) complexes are used as perfluoroalkylating agents, which react smoothly with arenediazonium salts to produce various perfluoroalkylarenes in good yields. Based on the results of clock trapping experiments with diallyl ether, a radical process might be involved in the reaction.

Abstract: Wittig reaction of aldehydes with difluoromethyltriphenylphosphonium bromide leading to gem-difluoroolefins in moderate yields is described. The reaction displays a good substrate scope including aryl, heteroaryl and α,β-unsaturated aldehydes. Difluoromethyltriphenylphosphonium bromide could be easily prepared and stored for a long time under air atmosphere. The salt exhibits high thermal stability demonstrated by thermogravimetric analysis. Its structure was confirmed by NMR spectroscopy and single crystal X-ray analysis.

Abstract: The preparation conditions and purification reaction mechanism for H₂–HF treatment of molten FLiNaK salt were investigated. The optimal process conditions for preparation of high-purity molten FLiNaK salt were obtained. They are purification temperature of 650 °C, liquid height of 0.9 m, purification time of 48 h, flow ratio of H₂/HF = 10, flow volume magnitude of 800 mL/min, and reaction pressure of 0 MPa. The oxygen content of the prepared molten salt was around 80 ppm, corrosion impurity elements (Cr, Fe, and Ni) were less than 20 ppm, and the S and P contents were below 5 ppm. The quality of FLiNaK molten salt prepared by this hydrofluorination process is better than that obtained by adding NH₄HF₂ as a fluorinating reagent.

Abstract: A copper-mediated trifluoromethylation of propargyl acetates with S-(trifluoromethyl)diphenylsulfonium triflate leading to trifluoromethylated allenes in moderate to excellent yields is described.

Abstract: The decarboxylation of potassium 2-pyridinyl sulfonyldifluoroacetate and its subsequent reaction with aldehydes was found to be an efficient approach for the Julia–Kocienski reaction under mild conditions to give gem-difluoro olefins in moderate to excellent yields. Owing to its high stability in the pure state and its easy decarboxylation in polar solvents, potassium 2-pyridinyl sulfonyldifluoroacetate is expected to be an efficient gem-difluoro-olefination reagent.

Abstract: Boron trihalide-promoted ring-opening reactions of gem-difluorocyclopropyl ketones to give the corresponding β-trifluoromethyl ketones and β-halodifluoromethyl ketones were described. It was found that boron trihalides act as both Lewis acids and nucleophiles and the proximal bond prefers to cleave in this transformation.

Abstract: Rhodium-catalyzed allylic C–F bond activation via oxidative addition was found to be a promising approach for the conversion of allylic difluoro-homoallylic alcohols into trisubstituted monofluoroalkenes in good yields with excellent stereoselectivity. The mechanism study shows that C–F bond activation via oxidative addition is involved and PPh3 is responsible for the excellent stereoselectivity.

Abstract: Tetrafluoroethane β-sultone (TFES) has hundreds of useful fluorinating derivatives as reagents. The reactions of TFES with nucleophiles provide a variety of interesting fluoroalkylsulfonic acids and their derivatives, as well as ω-halo-perfluoropentanesulfonyl fluorides. Fluorosulfonyldifluoroacetic acid derivatives such as FSO₂CF₂COOH, FSO₂CF₂COOMe, FSO₂CF₂COOTMS, HCF₂SO₂R (R = F, OH, OCF₂H, OC₆H₅), ICF₂SO₂F, and RCF₂OCF₂CF₂SO₂F (R = CF₂I, CO₂Me, CO₂Na) are versatile difluoromethylation and/or trifluoromethylation reagents. FSO₂CF₂COOH, FSO₂CF₂COOMe, FSO₂CF₂COOTMS, HCF₂SO₂R, and ICF₂SO₂F can effectively incorporate a CF₂ group into O H, N H, S H, C C, and C C bonds. HCF₂SO₂R (R = OH, OCF₂H, OC₆F₅) and FSO₂CF₂CO₂H generate difluorocarbene under acidic conditions, which significantly expanded the scope of the carbene-based difluoromethylation reactions. FSO₂CF₂CO₂Me, FSO₂CF₂I, and RCF₂OCF₂CF₂SO₂F (R = CF₂I, CO₂Me, CO₂Na) are powerful trifluoromethylation reagents, with FSO₂CF₂CO₂Me being world-renowned and widely used in the design of drug candidates and synthesis of novel functional materials. FSO₂CF₂CO₂Me, FSO₂CF₂I, and RCF₂OCF₂CF₂SO₂F are generally produced by nucleophilic substitution, thermal decomposition, or single-electron transfer mechanism in trifluoromethylation reactions under mild conditions. FSO₂CF₂CF₂OCF₂CO₂Me can successfully trifluoromethylate unactivated aryl chlorides with CuI, and FSO₂CF₂CF₂OCF₂CO₂K/CuI can smoothly transform aryl halides at very low temperature. For more than half a century's development, the chemistry of TFES and its derivatives has been extensively studied. This review recounts the recent progress of TFES and reports on TFES-derived difluoromethylation and trifluoromethylation reagents. The syntheses and reactivities of these interesting reagents, as well as their applications in medicinal chemistry and materials science, are briefly summarized.

Abstract: We have developed an efficient method to achieve N-gem-difluorocyclopropylation of N-heterocycles with the use of gem-difluorocyclopropyl tosylate as a building block under mild conditions. gem-Difluorocyclopropyl tosylates could be easily prepared on a large scale and exhibit great stability.

Abstract: CF3-containing esters smoothly reacted with electron-deficient alkenes in the presence of a phosphine (2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl) organocatalyst at room temperature in an aerobic atmosphere. These Michael reactions efficiently provided products with a CF3 quaternary carbon center.

Abstract: X(CF₂CF₂)nOCF₂CF₂SO₂F (X=I, Br, Cl; n=1, 2, 3, 4) are widely used fluoroalkylation reagents, which can incorporate ‘heavy’ fluorous tags into organic compounds. X(CF₂CF₂)nOCF₂CF₂SO₂F have both sulfonyl and halo groups. They behave as bi-functional fluoroalkylation reagents. The cleavage of the C–I bonds of I(CF₂CF₂)nOCF₂CF₂SO₂F by reductants (such as Na₂S₂O₄, Zn), single electron transfer reagents and radical initiator systems (like Bz₂O₂, AIBN, and (t-BuO)₂, or under UV and heat) gives, respectively, the sulfinatodehalogenated products, the hydrodehalogenated products, the homo-coupling products and the perfluoroalkylated products (if alkenes, alkynes or arenes were added). The functionalization of the sulfonyl groups (SO₂F) of X(CF₂CF₂)nOCF₂CF₂SO₂F by esterification, amidation, and fluorination affords the corresponding perfluoroalkanesulfonates, fluoroalkanesulfonamide, and perfluoroalkanes. In many cases, both the halo and sulfonyl groups of X(CF₂CF₂)nOCF₂CF₂SO₂F are transformed. These transformations finally lead to hundreds of useful highly fluorinated materials, such as supper acids, catalysts, surfactants, ion-exchange resins, electrolytes, polymers, and dense ionic liquids. Furthermore, X(CF₂CF₂)nOCF₂CF₂SO₂F have commendable advantages, such as the easy preparation, the wide range of substrate tolerance, the mild reaction condition, and the high yields of desired products, which make them very promising. This review briefly summarizes the synthesis, reactivity, and applications of these intriguing reagents.

Abstract: An efficient method for the copper-catalyzed trifluoromethylation of terminal alkenes with an electrophilic trifluoromethylating reagent has been developed. The reactions proceeded smoothly to give trifluoromethylated alkenes in good to excellent yields. The results provided a versatile approach for the construction of Cvinyl–CF₃ bonds without using prefunctionalized substrates.

Abstract: The chloroacetic acid/sodium hydroxide buffer system was applied in the determination of rare earth by photometric analysis. With Arsenazo III as chromogenic reagent, the sensitivity of various buffer systems was explored, including chloroacetic acid/sodium hydroxide, formic acid/sodium hydroxide and acetic acid/sodium acetate. The optimal conditions for the determination of lanthanide ions in chloroacetic acid were found and the corresponding molar absorptivities, were calculated. The results of photometric analysis which can be determined simply and quickly, were agree with the data of ICP-AES.

Abstract: The interconversion between difluoromethylene ylide and difluorocarbene is described. The difluoromethylene ylide precursor, Ph₃P⁺CF₂CO₂⁻, could be turned into an efficient difluorocarbene reagent, whereas the classical difluorocarbene reagents, HCF₂Cl and FSO₂CF₂CO₂TMS, could generate highly reactive difluoromethylene ylide. Thus the Wittig difluoro-olefination and difluorocyclopropanation could be selectively realized by using the same reagent. In addition, the ylides obtained from different carbene sources showed different reactivity in Wittig reactions.

Abstract: TheCF₃SO₃H-promoted ring opening of gem-difluorocyclopropyl ketones prefers to undergo proximal bond cleavage and the subsequent cyclization with nitriles occurred smoothly to give 2-fluoropyrroles.

Abstract: A key intermediate, difluoromethylene phosphobetaine, in the Wittig reaction of ClCF₂CO₂Na–Ph₃P with aldehydes was synthesized and characterized, which confirmed the reaction mechanism. The decarboxylation of this stable intermediate was a convenient approach for Wittig difluroolefination. Its reactivity could be adjusted by the modification of the substituent on the phosphorus.

Abstract: The copper-mediated trifluoromethylation of terminal alkynes with S-(trifluoromethyl)diarylsulfonium salt has been carefully investigated. The reactions proceeded smoothly to afford trifluoromethylated acetylenes in moderate to good yields. This approach is a convenient method to synthesize a variety of functional trifluoromethylated acetylenes.

Abstract: Well-defined polystyrene-co-poly(2, 3, 4, 5, 6-pentafluoro styrene) (PS-co-PPFS) copolymers were synthesized by atomic transfer radical polymerization (ATRP) in trifluorotoluene, fluorinated ionic liquid and trifluorotoluene/fluorinated ionic liquid solvent systems, respectively. The chain structure and component of such copolymers were characterized by 1H NMR, 19F NMR, elemental analysis and GPC. Porous films of PS-co-PPFS copolymers were fabricated by static breath-figure method in CS₂, CHCl₃ and CH₂Cl₂, respectively. The morphologies of such porous films were observed by scanning electron microscopy (SEM) and compared with those of PS homopolymer with similar molecular weight. The results showed that PS-co-PPFS copolymers with narrow molecular weight distribution (Mn=5200~7900 g • mol-1, Mw/Mn= 1.12~1.22) can be synthesized via ATRP in trifluorotoluene and fluorinated ionic liquid, respectively. The SEM observation indicated that PS-co-PPFS copolymer porous films can be fabricated with CS₂, CHCl₃ and CH₂Cl₂ as solvent, respectively. While, different from PS analogues, PS-co-PPFS copolymer porous films showed less ordered pore structures with two different average pore sizes. The pores of such film fabricated in CHCl₃ were in better order with two average pore sizes of 0.75 and 0.37 μm, respectively.

Abstract: A strategy for building coordination cages by a [6 + 8] condensation of MII4-calix SBUs and rigid ancillary ligands was successfully applied to a cobalt–sulfonylcalix[4]arene system. A giant cage obtained with BTE ligands has an overall periphery diameter of 5.0 nm and an internal spherical cavity of 2.3 nm.

Abstract: An organocatalytic asymmetric method for the synthesis of 2-CF₃ tetrahydroquinoline has been achieved. The cascade reaction of 2-aminochalcones with β-CF₃ nitroalkenes afforded the products bearing three contiguous stereogenic centers in good yields with excellent diastereoselectivities and enantioselectivities.

Abstract: The sulfinatodehalogenation reaction represents one of the most important methodologies to incorporate fluorine into organic molecules. Using inexpensive sulfur-containing reactants such as Na₂S₂O₄ under mild conditions, per- and polyfluoroalkyl halides (RFX, X = Br, I, CCl₃) can be transformed smoothly into the corresponding sulfinate salts. This method is also used for the perfluoroalkylation of alkenes, dienes, alkynes and aromatics. Notably, after 1998, the sulfinatodehalogenation of perfluoroalkyl chlorides (RFCl) has been realized by using dimethylsulfoxide (DMSO) as a solvent instead of CH₃CN/H₂O in the Na₂S₂O₄/NaHCO₃ initiation system. Perfluoroalkyl chlorides, ethyl chlorofluoroacetates and chlorodifluoroacetates, and even nonfluorinated compounds, such as ethyl chloro- or dichloroacetates and chloroform, were either converted into the corresponding sulfinate salts or alkylated alkenes, alkynes and aromatics (including porphyrins). The sulfinatodehalogenation reaction has remarkable advantages. With the increasing demands to utilize the unique properties of fluorine and fluorinated functional groups in medicinal, agricultural and material sciences, we believe that there will continue to be useful developments in sulfinatodehalogenation chemistry and it will be applied more widely in the future.

Abstract: Experimental studies showed that Ni(II) N-confused porphyrins, treated with fluoroalkylarylsulfonium salts, can undergo an electrophilic fluoroalkylation at the inner 21-C position, leading to 21-fluoroalkylated Ni(II) N-confused porphyrins.

Abstract: 1-Alkyl-3-methylimidazolium fluorides were successfully synthesized by the reaction of silver fluoride with the corresponding imidazolium iodides.

Abstract: Aldol reaction between simple benzaldehydes and ketones successfully happened in solvent- and catalyst-free condition. The desired products were obtained in moderate yield at suitable temperature. Heat was assumed as the driving force for the reaction. This approach has obvious advantages to fully meet the requirement of the principles of green chemistry.

Abstract: The enantioselective Friedel–Crafts fluoroalkylation of indoles with fluoroalkylated nitroalkenes, catalyzed by chiral phosphoric acid is described. The regioselectivity of fluoroalkylated nitroalkenes is a problem worth discussing, and it was found that the carbon atom adjacent to the fluoroalkyl group is more reactive than that adjacent to NO₂ group.

Abstract: The ligand-free trifluoromethylation of arylboronic acids with a [Ph₂SCF₃]+[OTf]−/Cu(0) system has been carefully investigated. Aryl-, alkenyl- and heteroarylboronic acids with a variety of functional groups were suitable substrates for this reaction. It is suggested that a CuCF₃ species is formed under the reaction conditions.

Abstract: Chiral N-heterocyclic carbene catalyzed annulations of ynals and enals with 1,3-dicarbonyls have been described. The two reactions provided direct and efficient methods for enantioselective synthesis of functionalized dihydropyranones. Comparatively, the reactions starting from ynals were atom-economical; furthermore the reactions of enals demonstrated broader substrate compatibility.

Abstract: The CF₃ radical was generated from the reaction of S-(trifluoromethyl)diphenylsulfonium triflate with Na₂S₂O₄ or HOCH₂SO₂Na under suitable conditions without further reduction. Based on this, a method for the synthesis of α-trifluoromethylated ketones has been successfully developed.

Abstract: We thank the Chinese Academy of Sciences (Hundreds of Talents Program), the National Natural Science Foundation (20972179, 21032006), Merck Research Laboratories, and the Syngenta PhD Studentship Award for financial support. We thank Dr. John Clough of Syngenta at Jealott’s Hill International Research Centre and Dr. Shubin Liu of University of North Carolina for proofreading of the manuscript.

Abstract: Monofluorovinyl tosylate was developed as a practical vinyl fluoride building block to couple with a variety of arylboronic acids in the presence of a palladium catalyst. The high stereoselectivity of 2-aryl-1-fluoroethene derivatives was achieved. This approach is also applicable to the synthesis of 2,2-diaryl-1-fluoroethenes in good yields.

Abstract: Both experimental and computational approaches have been employed in the present work to investigate the thermal conversion of substituted difluoro(methylene)cyclopropanes (F2MCP) E-1,1-difluoro-2,2-dimethyl-3-tosylmethylene cyclopropane 1, to the thermodynamically more stable F2MCP products, 1,1-difluoro-2-tosyl-3-(propan-2-ylidene)cyclopropane 2, and 1-(3-(difluoromethylene)-2,2-dimethylcyclopropylsulfonyl)-4-methylbenzene 3. The X-ray crystal structure has been obtained for both 1 and 2, respectively, based on which theoretical analyses on their structure and stability have been carried out. Possible reaction mechanisms are proposed.

Abstract： A series of new bis(fluoroalkanesulfonyl)imide based ionic liquids were synthesized in a one-pot procedure. These ionic liquids have high density, low glass transition temperature and high decomposing temperature, indicating a wide range of liquid state.

Abstract: The N-heterocyclic carbene-catalyzed reaction of alkynyl aldehydes with 1,3-keto esters or 1,3-diketones has been studied. This protocol offers an entirely new, mild and atom-economical access to highly functionalized 3,4-dihydropyranones.

Abstract: A series of bis(fluoroalkanesulfon)amides were synthesized in good yield from the reaction of fluoroalkanesulfonamides and fluoroalkylsulfonyl fluorides. Ionic liquids based on these amide anions and an imidazolium cation demonstrated high densities and a wide temperature range for the liquid state.

Abstract: Experimental studies demonstrated that alcohols and amines can undergo a CF₃COOAg-catalyzed nucleophilic addition at the outer C═N position of Ag(III) NCPs, leading to C-3-alkoxylated Ag(III) NCPs, which supports the computational result that the C═N bond on the periphery of Ag(III) NCPs is partially isolated from the 18 π-electron macrocyclic conjugation system and is the active electrophilic center.

Abstract: The pKa values of a series of fluoroalkanesulfonylamides were measured by potentiometric titration. Different kinds of alkyl halides and tosylates were employed to investigate the nucleophilicity of fluoroalkanesulfonylamides. Fluoroalkanesulfonylamides with longer fluoroalkyl chain have weaker nucleophilicity.

Abstract: S-(fluoroalkyl)diphenylsulfonium salts have been successfully synthesized from the reaction between fluoroalkylsulfinates and triflic anhydride in dichloromethane through a one-pot procedure. These S-(fluoroalkyl) diphenylsulfonium salts have been demonstrated to be effective reagents to fluoroalkylate C-nucleophilic substrates. Ionic substitution and radical or halogenophilic mechanism might be all involved in the reactions.

Abstract: Arylfluoroalkylsulfoxides were successfully synthesized in one-pot when fluoroalkylsulfinate reacted with benzene and triflic anhydride in triflic acid and dichloromethane as the medium. The characteristics of their 19F NMR spectra were examined and analyzed for these structures. Electronic and steric effects of substituents at α- or β-position were revealed to be the main cause of the anomalous behavior of their chemical shifts and coupling constants. Interactions between arylfluoroalkylsulfoxides and solvents were also investigated and discussed.

Abstract: Since the first synthesis of tribenzosubporphyrine in 2006, the chemistry of subporphyrins has attracted great interest. Recently, many methods have been developed to synthesize multiple-substituted subporphyrins. It is notable that the preparation of subporphyrin through the metathesis of expanded porphyrin is an effective way. Subporphyrin possesses a 14π conjugation system and C 3 symmetric bowl arrangement. The properties of subporphyrins such as UV-Vis spectra, fluorescence and substituent effects, are much different from those of normal porphyrins, which can be well explained by a four obital model, theoretical calculations and X-ray single crystal analysis. The subporphyrins bearing large meso-aryl groups exhibited some interesting properties including higher energy transfer efficiency, enhanced fluorescence intensity and two-photon absorption. Such modified subporphyrins have great potential applications to electronics and optics.

Abstract: Water was found to be a suitable reaction medium for the direct asymmetric aldol reaction of various cyclic ketones with aryl aldehydes catalyzed by a primary-tertiary diamine-Brønsted acid.

Abstract: A new precursor of N-heterocyclic carbene bearing push-pull substituents has been synthesized by the quaternization of 1-(4-methoxyphenyl)-imidazole. Unexpected reactions between the carbene generated in situ and aromatic aldehydes or acrylates were observed resulting in the formation of imidazole derivatives.

Abstract: Difluorocarbene generated from FSO₂CF₂CO₂SiMe₃ (TFDA) at 120 °C could reacted with terminal alkynes having an ester group at the α position to the triple bond. Difluorocyclopropenes were further converted to difluorocyclopropyl ketones under alkaline condition. Mechanism for the conversion was studied.

Abstract: A mild hydrodehalogenation reaction of fluoroalkyl halides (R_fCF₂X, X = Br, I) has been developed under weakly basic conditions, giving the corresponding hydrogenolysis products with moderate to high yields.

Abstract: The oxidation of Ni(II) N-confused porphyrins (NCPs) with azo radical initiators resulted in an unexpected intramolecular nucleophilic substitution reactionvia a proposed Ni(III) NCP intermediate, which could be detected by HRMS.

Abstract: A series of pyrrolidinium-based salts with new fluorine-containing anions were synthesized. Different melting points could be obtained by changing the length of the fluoroalkyl chain of the anions. The pyrrolidinium 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonate ([C₄H₈NH₂][H(CF₂)₄O(CF₂)₂SO₃]) is highly fluid even below room temperature. It can be used both as a recyclable solvent and as an efficient catalyst for Friedel–Crafts alkylations of indoles with nitroalkenes.

Abstract: An efficient method was developed for the synthesis of pentafluoroiodoethane from chloropentafluoroethane. Sulfinatodechlorination of CF₃CF₂Cl was carefully investigated. Subsequent iodination can be conducted in one pot without further purification, giving the corresponding CF₃CF₂I in practically acceptable yield.

Abstract: The first fluoroalkylated Ni(II) N-confused porphyrins were synthesized with high regioselectivity and its further alkylation was studied.

Abstract: The distal and proximal bond of difluoro(methylene)cyclopropanes (F₂MCPs) could be cleaved, respectively, under different conditions to give the corresponding ring-opening products. The reaction mechanisms are discussed.

Abstract: We synthesized several novel low-melting ionic salts with donor–acceptor substituents and investigated their possible applications as second-order nonlinear optical materials.

Abstract: Difluoro-substituted spirocyclopropaneisoxazolidines were formed by 1,3-dipolar cycloaddition of difluoro(methylene)cyclopropanes (F2MCPs) with nitrones in high yields. The [3+2]-cycloaddition reactions exhibited good regioselectivity and high stereoselectivity. The cycloadducts could rearrange further to form highly substituted 3,3-difluorinated tetrahydropyridinols

Abstract:Hexamethylphophoramide (HMPA) reacted with hexafluorobenzene and its derivatives with good conversion to give dimethylaminated products and phosphorofluoridates, even in unfavorable reaction stoichiometries. An aromatic nucleophilic mechanism might be involved.

Abstract:The Diels–Alder reactions of difluoro(methylene)cyclopropanes (F2MCPs) with cyclic dienes are described. These cycloaddition reactions exhibited complete regioselectivity and high endo-stereoselectivity. The obtained cycloadducts underwent a retro-Diels–Alder reaction to give the original dienophiles and dienes when heated, reflecting the reversible Diels–Alder reactivity of F2MCPs.

Abstract: A new class of geminal dicationic ionic liquids was formed with a bridging moiety, such as a polyalkyl ether, polyfluoroalkyl, 1,4-bismethylenebenzene, or 1,4-bismethylene-2,3,5,6-tetrafluorobenzene link, between alkyl-substituted imidazolium rings. Their properties were modified by varying the linker chains and/or alkyl substituents on the imidazolium ring. The polyfluoroalkyl bridged dicationic ionic liquids exhibit the highest densities and viscosities. Although melting points are directly proportional to the length of the alkyl substituent, the densities decrease concomitantly. With 1,4-bismethylene-2,3,5,6-tetrafluorobenzene as the linking chain and with longer alkyl substituents on the imidazolium rings, the nonpolar character of the ionic liquid greatly increases, e.g., the solubilities in toluene of dicationic ionic liquids 36 and 37, where the ring substituents are C₁₀H₂₁ and C₁₄H₂₉, increase markedly. Some of the salts exhibit higher conductivities than an equimolar tetrabutylammonium iodide solution in acetonitrile/toluene. These new ionic liquids (except with PF₆⁻ as anion) display outstanding tribological properties in temperature ramp tests by performing very well at 300 °C, thus meeting one criterion for high-temperature lubricants.

Abstract: 2,4,5-Trinitroimidazolate (TNI) salts with “high-nitrogen” cations tend to be highly hydrogen bonded and have heats of formation ranging up to 616 kJ mol⁻¹. Density, oxygen balance, and thermostability are enhanced by the presence of TNI. Based on theoretical calculations, all of the new salts are potential propellants.

Abstract: The reactions of 2-(2-pyridyl)imidazole with alkyl iodides at 25 degrees C in the presence of base gave rise to 1-alkyl-2-(2-pyridyl)imidazole. Subsequent neat reactions with alkyl or polyfluoroalkyl halides at 100 degrees C, followed by anion exchange with LiN(SO(₂)CF(₃))(2), generated the mono-quaternary ionic liquids. All of them have excellent thermal stability and wide liquid range. Most of the salts with asymmetric N-substituents are liquid at room temperature. The effect of N-substituent variation and symmetry on NMR, TGA and DSC is discussed. Reaction of with palladium(II) chloride produced a mononuclear palladium ionic liquid complex, the structure of which was confirmed by single-crystal X-ray diffraction analysis. The Heck cross-coupling reactions using in ionic liquid demonstrated excellent stability and recyclability.

Abstract: A basic ionic liquid was selected to serve as both the solvent and base for Heck, “copper-free” Sonogashira reactions, and for homocoupling reactions of terminal alkynes. The ionic liquids with tertiary aliphatic amines are effective solvents for these reactions. Under reflux conditions, eight equivalent basic ionic liquids and Pd(OAc)₂ in THF or acetone produced palladium colloids with diameters of (2.6 ± 0.3) or (3.7 ± 0.5) nm, respectively. Preliminary results for Knoevenagel condensations are also reported.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Abstract: A series of fluorinated meso,β-fused 5,15-diphenyl­porphyrins have been synthesized by the reaction of 5,15-di­phenylporphyrins with fluoroalkyl halides under modified sulfinatodehalogenation reaction conditions through radical cyclization.

Abstract: Difluoro(methylene)cyclopropanes (F₂MCPs) were prepared directly by difluorocarbene addition to allenes,and the resulting F₂MCPs were converted into a variety of difluoro(methylene)cyclopropane derivatives through Heck reactions and electrophilic substitutions. The ring-opening reactions of F₂MCPs with I₂ are reported and a plausible reaction mechanism is also discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA,69451 Weinheim,Germany,2006)

Abstract: We report three crystal structures of a synthetic 5-fluoroalkylporphyrin molecule that was programmed for self-assembly. All the X-ray structures of zincated and free-base porphyrins Zn₂ b, Zn₅ a, and 2 b revealed rigorous π–π stacking and extremely hydrophobic interactions. Other the other hand, the strong aggregation of 5-fluoroalkylporphyrins in solution was also found. Interestingly, the regular nanopore formation of the 5-fluoroalkylporphyrin was visualized by atomic force microscopy (AFM). Importantly, the 5-fluoroalkylporphyrins possess liquid-crystalline properties that were confirmed by using a combination of differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) techniques. By comparison, the self-assembly of non-fluorine-containing porphyrins with similar structure showed much lower aggregation ability, as investigated by NMR techniques. Additionally, no birefringent mesophase was observed for the non-fluorine-containing porphyrin.

Abstract: A series of 10,20-diaryl-5-[(E)-fluoroalkenyl]-15-(fluoroalkyl)porphyrins has been synthesized by the reaction of free-base 5,15-diarylporphyrins with fluoroalkyl iodides in the presence of Na₂S₂O₄. Subsequent intramolecular cyclization of the corresponding (fluoroalkenyl)porphyrins occurs smoothly in refluxing toluene/H2O. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Abstract: In the presence of sodium dithionite and DMSO, the intramolecular radical cyclization of 4-chloro-1,1,2,2,3,3,4,4-octafluorobutylbenzenes is achieved to give the corresponding cyclic compounds in moderate to good yields.

Abstract: A new room-temperature ionic liquid has been synthesized from 2,2'-bipyridine. This liquid improved the copper-catalyzed cross-coupling reactions between perfluoroalkyl or pentafluorophenyl halides and aryl iodides. Good recyclability using this solvent system was observed.

Abstract: Energetic ionic salts of azotetrazolate (AT), iminobis(5-tetrazolate) (IBT) and 5, 5′-bis(tetrazole) (BT) were synthesized; 1-methyl-4-aminotriazolium azotetrazolate has a layered structure and exhibits a heat of formation of +4360 kJ kg⁻¹.

Abstract: Neat reactions of 2,2‘-biimidazole with an excess of alkyl or polyfluoroalkyl iodides at 140 °C, followed by anion exchange with LiN(SO₂CF₃)₂ or KPF₆, gave the diquaternary salts 3a−k in >80% yields. However, by controlling the reaction stoichiometry, 2,2‘-biimidazole can also be monoquaternized with the same electrophiles at 100 °C under similar conditions. Subsequent metathesis reactions with LiN(SO₂CF₃)₂ or KPF₆ resulted in the ionic liquids 4a−m in high yields. Thermal properties were determined with a differential scanning calorimeter (DSC) and a thermogravimetric analyzer (TGA). Most of the monoquaternary salts are room-temperature ionic liquids. 1,3,1‘-Tributyl-2,2‘-biimidazolium hexafluorophosphate was demonstrated to be an excellent solvent and ligand for palladium-catalyzed Suzuki cross-coupling reactions. The catalytic ionic liquid system may be recycled at least 14 times without a significant decrease in catalytic performance.