Article
Chemistry, Organic
Cheng Wu, Xiao Shen, Jianjun Dai, Jun Xu, Huajian Xu
Summary: By utilizing a direct nucleophilic substitution reaction under transition metal free conditions, easily available aryl and alkyl thiocyanates were converted into the desired products, enabling the synthesis of (benzenesulfonyl)difluoromethyl thioethers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Applied
Xin Qiu, Wenrun Lou, Shengxue Zhang, Shengyajun Meng, Yong Guo, Xiaoyu Ma, Chao Liu, Qilong Shen
Summary: A convenient method for the preparation of the efficient radical difluoromethylthiolation reagent PhSO2SCF2H was reported. The reagent was synthesized on a scale of approximately 500 g from cheap commodity sodium benzene sulfinate, benzyl mercaptan, and HCF2Cl in two steps. The key step of this method involves controlling the amount of chlorine and reaction temperatures to generate the key intermediate [HCF2SCl]. The stability of PhSO2SCF2H was confirmed by differential scanning calorimetry (DSC). Additionally, gram-scale reactions of PhSO2SCF2H with electron-rich aromatic (hetero)-hydrocarbons, alkyl carboxylic acids, and olefins were demonstrated.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Review
Chemistry, Multidisciplinary
Jonathan Decaens, Samuel Couve-Bonnaire, Andre B. Charette, Thomas Poisson, Philippe Jubault
Summary: This Minireview discusses recent progress in synthesizing fluoro-substituted three-membered rings and reports the main synthetic methodologies for cyclopropanes since 2016 and for other three-membered rings since 2010.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Sen Zhou, Xiaoya Hou, Kai Yang, Minjie Guo, Wentao Zhao, Xiangyang Tang, Guangwei Wang
Summary: A novel method for synthesizing N-difluoromethyl-2-pyridones from readily available pyridines has been described, utilizing mild reaction conditions and identifying N-difluoromethylpyridinium salts as key intermediates in the conversion process.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Huahong Chen, Shunli Wen, Yubo Cui, Lu Lin, Hanbang Zhang, Zheng Fang, Yi You, Zhiqiang Weng
Summary: A method for the synthesis of polysubstituted 4-difluoromethyl and perfluoroalkyl pyrazole derivatives has been reported using Lewis acid- and base-co-mediated reaction. A series of structurally diverse pyrazoles were obtained in moderate to good yields. The reactions proceeded smoothly under mild conditions with wide functional group tolerance.
Article
Chemistry, Analytical
Zhiyang Tang, Zhongqi Hao, Ran Zhou, Qingzhou Li, Kun Liu, Wen Zhang, Jiujiang Yan, Kaiwen Wei, Xiangyou Li
Summary: By combining calcium with F and Cl in samples to synthesize CaF and CaCl molecules, a high sensitivity detection of chlorine and fluorine elements in water was achieved using molecular emission. The results show the potential of LIBS assisted with molecular synthesis in water quality monitoring.
Article
Chemistry, Organic
Wenjuan Zhu, Hui Xi, Wenyang Jiao, Lihua Huang, Lianjie Wang, Junliang Wu
Summary: A visible-light-promoted alkoxysulfonylation of gem-difluoroalkenes using sulfonyl chlorides and alcohols has been developed. The reaction shows a broad substrate scope and excellent functional group compatibility. This method involves an atom transfer radical addition-like process, and the products can serve as platform molecules for further modification.
Article
Chemistry, Multidisciplinary
Amelia Messara, Armen Panossian, Koichi Mikami, Gilles Hanquet, Frederic R. Leroux
Summary: The deprotonative functionalization of alpha,alpha-difluoromethyl ketones is achieved by using a catalytic organosuperbase and a silane additive, leading to the generation of difluoroenolates that can be trapped with aldehydes to produce alpha,alpha-difluoro-beta-hydroxy ketones. This strategy allows for the direct deprotonation of the difluoromethyl unit and is tolerant of various functional groups. The diastereoselective version of the reaction was also explored, with high diastereomeric ratios. Several transformations demonstrate the synthetic potential of these alpha,alpha-difluoro-beta-hydroxy ketones. Additionally, the method can be extended for the use of other electrophiles and nucleophiles, resulting in a diversity of difluoromethylene compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Geochemistry & Geophysics
Lillian A. Kendall-Langley, Anthony I. S. Kemp, Chris J. Hawkesworth, Eimf, Malcolm P. Roberts
Summary: Apatite inclusions hosted by zircon can be used to probe the magmatic history and volatile budgets of granitic rocks. Variations in Cl and F concentrations in melts among different granitic suites are attributed to differences in source compositions. Moreover, the study found that melt F and Cl concentrations decrease with magmatic differentiation and falling melt temperatures.
CONTRIBUTIONS TO MINERALOGY AND PETROLOGY
(2021)
Article
Chemistry, Multidisciplinary
Andreas Billion, Jonas Schulte, Andreas Vogel, Felix Hilfinger, Ingo Krossing
Summary: A novel continuous route for synthesizing oxymethylene dimethyl ethers (OMEn) by the reaction of molecular formaldehyde and dimethyl ether is presented. Acidic, porous, and thermally stable zeolites proved to be effective catalysts for this reaction. The results contribute to a better understanding of the complex reaction network in the OMEn synthesis and provide important insights for establishing an energy efficient and sustainable OMEn production process.
Article
Chemistry, Organic
Xuemin Li, Yue Li, Jingyue Yang, Haofeng Shi, Zhenkang Ai, Chi Han, Jiaxin He, Yunfei Du
Summary: In this study, the reaction of alkynyl aryl ketones with difluoromethyl sulfoxide in the presence of Tf2O conveniently yielded 3-SCF2H-substituted chromones. This represents the first reagent system capable of introducing the biologically important SCF2H moiety under base-free conditions via an interrupted Pummerer reaction. The same protocol could also be used to synthesize 3-SCF3-substituted chromones.
Article
Chemistry, Organic
Chen-Yuan Li, Zengyu Zhang, Xiaoyu Yan
Summary: This study presents a novel strategy for postmodification of difluoromethyl compounds. Ortho-selective C-H borylation of difluoromethyl arenes is achieved by a cyclometalated mesoionic carbene-Ir complex. The regioselectivity is controlled by a hydrogen bond between CF2H and the boryl group via the outer-sphere direction.
Article
Chemistry, Multidisciplinary
Shivashankar Khanapur, Kenneth Lye, Dipendu Mandal, Xin Jie Wee, Edward G. Robins, Rowan D. Young
Summary: We present a general method for labeling both CF3 and CF2H groups in various chemical settings. The method provides good radiochemical yields and molar activities, and is applicable to biologically relevant compounds. The use of target compounds as starting materials and the simplicity of the method make it attractive for drug and radiotracer development.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Xiaojia Cai, Jinyuan Xu, Xueli Cui, Jing Qu, Weiqiang Sun, Jinhui Hu, Shuwen Zhao, Wen-Hua Chen, Hongliang Li, Jia-Qiang Wu
Summary: Herein, we developed a sustainable and efficient method for the synthesis of a series of alpha,alpha-difluoromethyl carbinols from the remarkable Friedel-Crafts reaction of electron-rich arenes including indoles, phenols, and anilines with easily accessible 2,2-difluorovinyl arylsulfonates in trifluoroethanol. This method is characterized by its simplicity, wide substrate scope, and excellent functional group tolerance.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Xiaorui Jiao, Zhonghou Huang, Weidong Meng, Shengqing Zhu, Lingling Chu
Summary: A catalyst-free and mild visible-light-induced reductive defluoroallylation of difluoromethyl ketones with allylic chlorides is presented, providing efficient access to α-fluoro alkenylketones. The alkyl amines play a dual role in this reaction as both electron donors for selective C-F bond cleavage of CF2H-ketones and halogen-atom transfer agents for activation of the C-Cl bond in allylic chlorides. The protocol shows a broad substrate scope and synthetic derivatizations of the resulting α-fluoro alkenylketones as well as preliminary mechanistic studies are discussed.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Xianda Wu, Minghong Chen, Shuiyun Zheng, Fu-Sheng He, Jie Wu
Summary: Here, we report a new method for synthesizing sulfilimines through an iron-catalyzed reaction between sulfenamides and 2,2,2-trifluor-diazoethane. This protocol features operational simplicity, mild conditions, and can be conducted in open air, providing a facile approach to trifloromethylated sulfilimines in moderate to good yields.
JOURNAL OF FLUORINE CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Ita Hajdin, Romana Pajkert, Haibo Mei, Jianlin Han, Gerd-Volker Roeschenthaler
Summary: A catalyst- and solvent-free 1,3-dipolar cycloaddition reaction using a bench-stable diazo reagent has been developed to obtain a series of novel 3H-pyrazoles bearing difluoromethyl phosphonate unit in moderate-to-excellent yields. This method provides an efficient and easy route to synthesize valuable compounds.
JOURNAL OF FLUORINE CHEMISTRY
(2024)