Article
Chemistry, Organic
Bingbin Zhu, Hang Han, Wei-Ke Su, Boan Yan, Zhi Li, Chuanming Yu, Xinpeng Jiang
Summary: A metal-free intramolecular carbofluorination protocol for the synthesis of tetrasubstituted monofluoroalkenes from internal alpha,beta-ynones and Selectfluor is reported, demonstrating high stereoselectivity and broad functional group tolerance. Chelation between tetrafluoroborate anion and the aldehyde group oxygen enhances stereoselectivity, with tetrafluoroborate serving as the direct fluorine source. Furthermore, the addition of sodium tetrafluoroborate allows for multiple reuse of Selectfluor without loss of reactivity.
Article
Chemistry, Organic
Ran Liu, Jinbo Hu
Summary: In this study, aryl perfluorocyclopropyl ethers were synthesized for the first time via a [2 + 1] cyclopropanation reaction between aryl trifluorovinyl ethers and TMSCF2Br reagent. The reaction proceeded smoothly under suitable conditions and demonstrated tolerance to various functional groups.
Review
Chemistry, Multidisciplinary
Paulo H. S. Paioti, Stella A. Gonsales, Shibo Xu, Ali Nikbakht, Diana C. Fager, Qinghe Liu, Amir H. Hoveyda
Summary: Stereochemically defined organofluorine compounds play a vital role in drug discovery. This article discusses various strategies and techniques for accessing these compounds selectively. One approach involves incorporating a fluorine atom or an organofluorine moiety into the compound, while another approach utilizes commercially available compounds with fluorine atoms. The authors highlight the potential of alkenyl and allylic fluorides in the preparation of stereochemically defined fluoro-organic molecules and emphasize the untapped opportunities for therapeutic science.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Katerina Kucnirova, Jaroslav Kvicala, Martin Svoboda, Josef Cvacka, Jan Cejka, Marketa Rybackova
Summary: The ring-opening cross metathesis (ROCM) of 3,3,4,4-tetrafluorocyclobutene with electronically rich alkenes, catalyzed by Grubbs or Hoveyda-Grubbs 2nd generation precatalysts, produced non-symmetrical isolated dienes with a tetrafluoroethylene spacer between the double bonds. These dienes underwent subsequent regioselective cross metathesis (CM) with styrenes, catalyzed by Hoveyda-Grubbs 2nd generation precatalyst, leading to non-symmetrically substituted dienes. The dihydroxylation and cyclization of 6,6-dibutoxy-3,3,4,4-tetrafluorohex-1-ene resulted in the formation of 3,3,4,4-tetrafluorohexopyranose.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Materials Science, Multidisciplinary
Jillian E. Moffatt, Thomas J. de Prinse, Georgios Tsiminis, Elizaveta Klantsataya, Thomas B. Payten, Lewis d. S. Teixeira, Barnaby W. Smith, David J. Ottaway, Nigel A. Spooner
Summary: Previous research has demonstrated that defect structures based on fluorine in calcium fluoride can emit visible-spectrum fluorescence when excited by UV light. This study reveals the behavior of a new fluorescence center emitting near infrared light (1100-1200 nm) when excited by visible light. This emission is most noticeable in natural fluorite samples with structural defects caused by long-term exposure to environmental radiation, but it can also be induced in a synthetic calcium fluoride sample using intense UV light. Excitation of the near-infrared emission is maximized near the previously reported F-centre aggregate absorption peak. The fluorescence measurement could be utilized to monitor defects in optical grade fluorite caused by high power lasers and have applications in fluorite mineral detection during mining operations. The potential resetting of these optical defects is also discussed.
Article
Chemistry, Organic
Anais Loison, Fabien Toulgoat, Thierry Billard, Gilles Hanquet, Armen Panossian, Frederic R. Leroux
Summary: The fluorine atom and fluorinated substituents play important roles in pharmaceutical and agrochemical active ingredients, beneficially modulating their properties. Among these, the -OCHF2 group is emerging as an interesting motif capable of forming hydrogen bonds. There is a growing need for methods to introduce this group.
Article
Chemistry, Physical
Isabel Pardo, David Bednar, Patricia Calero, Daniel C. Volke, Jiri Damborsky, Pablo I. Nikel
Summary: This study discovered a highly efficient nonconventional fluorinase and demonstrated its potential in increasing the production of fluoronucleotides in a bacterial host, paving the way for efficient biohalogenation.
Article
Engineering, Environmental
Shaowei You, Shaotao Cao, Chunyang Mo, Yi Zhang, Jianwen Lu
Summary: This study presents a new process for recovering high purity calcium fluoride from wastewater. A column reactor system with calcium sulfate dihydrate as reaction medium was used, resulting in the successful production of calcium fluoride with purity exceeding 99% and reducing fluoride concentration in wastewater to less than 10 mg/L. The process effectively removes fluoride while recovering high-purity calcium fluoride and various parameters such as initial fluoride concentration, flow rate, pH, and time significantly influence fluoride removal efficiency. The study offers an effective strategy for resource utilization and standard discharge of fluorine-containing wastewater.
CHEMICAL ENGINEERING JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Xavier Bertrand, Laurent Chabaud, Jean-Francois Paquin
Summary: This mini-review discusses various approaches for the hydrofluorination reaction of alkenes, including the use of HF complexes and different sources of fluorine. Research has shown that hydrofluorination reactions exhibit enantioselectivity and compatibility with a wide range of functional groups.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Takumi Kikumura, Koki Kamura, Takeshi Hanamoto
Summary: The synthesis of trifluoromethylated vinylsilane compound is described in this paper. The compound was readily prepared with a high yield using stereodefined (Z)-2-bromo-2-(trifluoromethyl)vinyl phenyl sulfide and chlorotrimethylsilane under Barbier-type reaction conditions. Furthermore, the reaction of the vinylsilane with various aldehydes successfully yielded the corresponding 2-(trifluoromethyl)allyl alcohol derivatives in moderate to good yields.
JOURNAL OF FLUORINE CHEMISTRY
(2022)
Article
Chemistry, Applied
Renxiang Liu, Xiao-Cong Zhou, Xin-Yi He, Yuan-Qiang Li, Weiqin Zheng, Xiu Wang, Junkai Guo, Chuanfa Ni, Jinbo Hu
Summary: This article presents a general and practical method for the preparation of the new fluorination reagent, SulfoxFluor, and its adaption to large-scale production. The method simplifies the process and reduces safety risks by using chloramine-T trihydrate instead of anhydrous chloramine-T. Furthermore, the research provides valuable insights into the imidation reaction of sulfinyl chlorides with chloramine-T in the presence of water.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Review
Chemistry, Organic
Marie Gonay, Chloe Batisse, Jean-Francois Paquin
Summary: This review summarizes recent advances in the preparation of acyl fluorides, including nucleophilic fluorination and radical fluorination methods, providing a reference for further research in the field of organic synthesis.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Zexian Li, Minyan Wang, Zhuangzhi Shi
Summary: An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed, generating valuable multisubstituted perfluoroalkylated compounds in a single step. Mechanistically, photoinduced alkyl radical addition to an alkene leads to migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center, followed by generation of a C-radical bearing two electron-withdrawing groups and reduction by a hydrogen donor to complete the domino sequence.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Utsab Manna, Gopal Das, Md Alamgir Hossain
Summary: This review provides a comprehensive assessment of examples of neutral receptors binding fluoride, focusing on the structural aspects. It discusses the selective solid-state capture of fluoride by various receptors and also briefly mentions the fluoride selective sensing in solution state.
COORDINATION CHEMISTRY REVIEWS
(2022)
Review
Chemistry, Multidisciplinary
Trevor W. Butcher, Willi M. Amberg, John F. Hartwig
Summary: Alkyl fluorides play a crucial role in medicinal chemistry, but their synthesis, especially chiral ones, remains challenging. In addition to fluorination methods, monofluoroalkylation has emerged as an effective strategy for synthesizing alkyl fluorides. Catalyzed by transition-metal complexes, this method provides a way to access chiral secondary and tertiary alkyl fluorides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Audrey Gilbert, Melodie Birepinte, Jean-Francois Paquin
Summary: A new method for adding SF5Cl onto unsaturated compounds was developed using an electron donor-acceptor (EDA) complex and visible light irradiation. Compared to common SF5Cl addition protocols, this reaction does not require the presence of oxygen to proceed. The method was successfully demonstrated on 19 examples of alkenes and alkynes, with yields ranging from 31% to 86%.
JOURNAL OF FLUORINE CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Xavier Bertrand, Laurent Chabaud, Jean-Francois Paquin
Summary: This mini-review discusses various approaches for the hydrofluorination reaction of alkenes, including the use of HF complexes and different sources of fluorine. Research has shown that hydrofluorination reactions exhibit enantioselectivity and compatibility with a wide range of functional groups.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Correction
Chemistry, Organic
Audrey Gilbert, Pauline Langowski, Marine Delgado, Laurent Chabaud, Mathieu Pucheault, Jean-Francois Paquin
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Melodie Birepinte, Pier Alexandre Champagne, Jean-Francois Paquin
Summary: This photoinitiated anti-hydropentafluorosulfanylation of terminal alkynes uses SF5Cl and (TMS)(3)SiH as the hydrogen atom donor. It selectively generates (Z)-(1-alken-1-yl)pentafluoro-lambda(6)-sulfanes, allowing for the preparation of a previously unknown geometrical isomer. DFT calculations show that the selectivity is due to the preference of SF5-substituted vinylic radicals to adopt a cis geometry and increased steric contacts during transition structures leading to the minor (E)-products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Raphael Gauthier, Nikolaos Tzouras, Ziyun Zhang, Sandrine Bedard, Marina Saab, Laura Falivene, Kristof Van Hecke, Luigi Cavallo, Steven P. Nolan, Jean-Francois Paquin
Summary: This study presents an efficient and chemoselective methodology using gold-N-heterocyclic carbene (NHC) complexes as catalysts for the hydrofluorination of terminal alkynes in aqueous HF. Mechanistic studies reveal the in situ generated catalyst formed by the reaction of Bronsted basic gold pre-catalysts with HF, showing highest reactivity and chemoselectivity. The catalytic system has a wide substrate scope, and computational studies aid in understanding the chemoselectivity observed through key mechanistic steps involving different gold species.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Xavier Bertrand, Pascal Paquin, Laurent Chabaud, Jean-Francois Paquin
Summary: The hydrochlorination, hydrobromination, and hydroiodination of unactivated alkenes using methanesulfonic acid and inorganic halide salts in acetic acid are reported, providing alkyl halides in high yields. An example of deuteriochlorination using deuterated acetic acid as the solvent is also demonstrated in this study.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Inorganic & Nuclear
Marie-Rose Ouellet-Du Berger, Maxim Boucher, Jean-Francois Paquin
Summary: A reagent-free activation method using blacklight compact fluorescent lamp irradiation was developed for the addition of SF5Cl on unsaturated compounds. A total of 19 examples of alkenes and alkynes were performed, with yields ranging from 25% to 99%. Overall, this method provides an oxygen-free alternative to the most common SF5Cl addition reaction conditions.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Vincent Mastalerz, Kevin Lam, Jean-Francois Paquin
Summary: The study explored a Kolbe-based reaction for the preparation of aliphatic SF5-compounds. Using 2-(pentafluoro-lambda 6-sulfanyl)acetic acid as the SF5CH2 source, it reacted with aliphatic carboxylic acid. Nine examples of unsymmetrical coupling were achieved, with NMR yields ranging from 15% to 66% (up to 62% isolated yield). Although the yields are modest, this method represents one of the few strategies to rapidly access aliphatic SF5-containing compounds.
JOURNAL OF FLUORINE CHEMISTRY
(2023)
Article
Chemistry, Organic
Lauriane C. Peyrical, Marie-Rose Ouellet-Du Berger, Maxim Boucher, Melodie Birepinte, Jean-Franccommaois Paquin, Andre B. Charette
Summary: The synthesis of trifluoromethyl (CF3)- and pentafluorosulfanyl (SF5)-substituted cyclopropane-fused gamma-lactones was achieved with high yields using Rh-2(esp)(2)-catalyzed intramolecular cyclopropanation. Twelve examples of this interesting scaffold were reported, along with postfunctionalizations to access highly functionalized CF3- and SF5-substituted cyclopropanes. These novel SF5-substituted analogues contribute to the limited list of available pentafluorosulfanyl intermediates.
Review
Chemistry, Multidisciplinary
Raphael Gauthier, Jean-Francois Paquin
Summary: This review explores recent advances in the hydrofluorination of diverse alkynes through various activation methods, from classical coinage metal catalysis to metal-free conditions. The method efficiently synthesizes monofluoroalkenes or difluoroalkanes, both of which have applications in medicinal chemistry and beyond. The range of alkynes covered includes unactivated alkynes as well as activated ones such as ynones and derivatives, ynamides, alkynyl sulfides and sulfones, and haloalkynes. Regio- and stereoselective methods exist, but there is still room for improvement depending on the type of alkyne.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Remy Ferlet, Mathieu Pucheault, Laurent Chabaud, Jean-Francois Paquin
Summary: The translation introduces a novel method for the preparation of molecules containing a monofluoroalkene core. By introducing a boryl nucleophile, polyvalent borylated intermediates can be obtained as versatile synthetic precursors. A nucleophilic substitution reaction of gem-difluoropropenes using a diborane/fluoride system was performed to achieve defluorinative functionalization without transition metals, and the reactivity was improved by using HMDS as an additive.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xavier Bertrand, Mathieu Pucheault, Laurent Chabaud, Jean-Francois Paquin
Summary: The combination of methanesulfonic acid and potassium bifluoride is reported for the deoxyfluorination of tertiary alcohols, achieving high yields of the corresponding fluorides and investigating the reaction mechanism. The application of these conditions for the fluorination of ether and ester is also demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Olivier Thibeault, Marie-Rose Ouellet-Du Berger, Marie Gonay, Jean-Francois Paquin
Summary: This study describes the synthesis of difluoromethyl-containing compounds by utilizing the deoxofluorination reaction of aromatic aldehydes using XtalFluor-E. The reaction takes place at room temperature under highly concentrated conditions, without the need for any additional solvent. A wide range of difluoromethyl-containing compounds were obtained with isolated yields ranging from 21% to 87%.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Raphael Gauthier, Nikolaos V. Tzouras, Steven P. Nolan, Jean-Francois Paquin
Summary: The gold-catalyzed hydration of 2,2,2-trifluoroethyl-substituted alkynes exhibits high regioselectivity, resulting in the formation of β-trifluoromethylketones as the major products. This transformation highlights the significant directing effect of the trifluoromethyl group, mediated by its inductive effect, in gold-catalyzed addition to alkynes.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Lauriane C. Peyrical, Marie-Rose Ouellet-Du Berger, Maxim Boucher, Melodie Birepinte, Jean-Francois Paquin, Andre B. Charette
Summary: Trifluoromethyl (CF3) and pentafluorosulfanyl (SF5) substituted cyclopropane-fused gamma-lactones were successfully synthesized through Rh2(esp)2-catalyzed intramolecular cyclopropanation, with yields up to 99%. Twelve examples of this interesting scaffold are reported, along with postfunctionalizations to access highly functionalized CF3- and SF5- substituted cyclopropanes. These novel SF5-substituted analogues join the limited list of available pentafluorosulfanyl intermediates.
