Article
Chemistry, Multidisciplinary
Hao Jia, Andreas P. Haering, Florian Berger, Li Zhang, Tobias Ritter
Summary: In this study, we report the synthesis and application of a novel trifluoromethylating reagent TT-CF3+OTf-, which can be used in various trifluoromethylation reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Hao-Zeng Wu, Zhong-Shan Teng, Yu-Xin Ke, Yu Zou, Ping Gao, Yue Li, Cheng-He Zhou, Zhong-Lin Zang
Summary: Tuning the electronic structure of protecting groups on the nitrogen atom of substrates has emerged as an effective strategy for achieving tandem trifluoromethylation/C(sp(2))-H annulation using Langlois' reagent as the CF3 source for electrochemical synthesis of functionalized tetrahydroquinolines and dihydroquinolinones.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Aleksey Zerov, Irina A. Boyarskaya, Olesya Khoroshilova, Irina N. Lavrentieva, Alexander Slita, Ekaterina O. Sinegubova, Vladimir V. Zarubaev, Aleksander V. Vasilyev
Summary: Trimethylsilyl ethers of 1,5-diaryl-3-(trifluoromethyl)pent-1-en-4-yn-3-oles in the superacid TfOH give rise to reactive conjugated CF3-allylic-propargylic cations, which, in the presence of arenes and excess TfOH, lead to the formation of E-1,1,5-triaryl-3-(trifluoromethyl)-pent-2-en-4-ynes and CF3-bicyclic dihydroanthracene derivatives, respectively. These two main reaction pathways are dependent on the nucleophilicity of aryl substituents in CF3-pentenynes and external aromatic molecules.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ru Zhong Zhang, Wanqiao Huang, Ru Xue Zhang, Cong Xu, Mang Wang
Summary: An efficient methodology for synthesizing a wide range of N-CF3 imidic acid derivatives is presented. The method involves the generation of N-CF3 nitrilium ions from nitriles using PhICF3Cl under catalysis with DMAP, followed by the capture of N-, O-, or S-centered nucleophiles to produce diverse N-CF3 amidines, imidates, and thioimidates. This method provides a platform for preparing N-CF3 compounds with potential applications.
Article
Chemistry, Multidisciplinary
Camila M. Kisukuri, Vitor A. Fernandes, Jose A. C. Delgado, Andreas P. Haering, Marcio W. Paixao, Siegfried R. Waldvogel
Summary: Electrosynthesis is a powerful and sustainable method for synthesizing small organic molecules, capable of generating highly reactive species under mild conditions. The installation of fluorinated alkyl groups, which has gained significant attention in medicinal chemistry and material science, presents a challenging transformation that has been addressed by several established electrochemical methods.
Article
Chemistry, Multidisciplinary
Leibing Wang, Jieping Wang, Sitao Ye, Beihan Jiang, Zihao Guo, Yasir Mumtaz, Wenbin Yi
Summary: A general and efficient synthesis of N-CF3 secondary amines has been reported, using in situ generated difluoromethyl imine intermediates and hydrogen fluoride produced by triethylsilane and silver fluoride. This method provides a new route for the synthesis of N-CF3 compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Han Wang, Yongbin Xie, Yicheng Zhou, Nannan Cen, Wenbo Chen
Summary: A new electrochemical strategy for trifluoromethylation/cyclization using TfNHNHBoc as a CF3 source has been developed. This approach involves the direct electrolysis of TfNHNHBoc under external oxidant-free and catalyst-free conditions, leading to the formation of various trifluoromethylated oxindoles with good functional group compatibility and broad substrate scope.
CHINESE CHEMICAL LETTERS
(2022)
Review
Chemistry, Applied
Cairong Wang, Ge Qiu, Chen Li, Kai Sun, Zhichuan Wang, Xin Wang
Summary: Carboxylic acid compounds are important structural units that exist widely in nature, and decarboxylative reactions have great significance in synthetic chemistry due to the non-flammable, non-toxic, and easy-to-remove byproduct carbon dioxide. Heterocyclic compounds are important backbones of various biologically active molecules, making research on new synthetic tactics for heterocyclic derivatives based on decarboxylative cyclization of great interest.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Physical
Xiangyu Li, Na Li, Lan Yang, Rui Jiang, Yong He, Jian Shi, Zhong-Xing Jiang, Zhigang Yang
Summary: This study demonstrates a method using metal catalysts to control switchable nucleophilic sites, and provides a strategy to construct CF3-containing thiazoles and allenes via a multicomponent reaction. The reaction is practical and convenient, compatible with various sensitive functional groups and shows high inhibitory activities against human cancer cell lines. The CF3-containing thiazoles increase the level of reactive oxygen species in MCF-7 cells, suggesting a potential mechanism for inducing tumor cell apoptosis.
Article
Chemistry, Multidisciplinary
Yuanqiang Guo, Ruiguo Wang, Hongjian Song, Yuxiu Liu, Qingmin Wang
Summary: The protocol described in this study utilizes electrochemical cathode reduction to generate trifluoromethyl radicals using an inexpensive and readily available trifluoromethylation reagent (IMDN-SO2CF3). The reaction can be efficiently conducted without the need for additional redox reagents, allowing for electrochemical trifluoromethylation/cyclization for the synthesis of isoquinoline-1,3-diones and oxindoles. This strategy demonstrates good functional group tolerance and a broad substrate scope.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Mingshi Pan, Yixin Tong, Xiaodong Qiu, Xiaobao Zeng, Biao Xiong
Summary: A method for accessing 3-trifluoromethyl-1,4-benzoxazines from CF3-imidoyl sulfoxonium ylides and 2-bromophenols has been demonstrated. This method proceeds through a one-pot two-step sequence involving O-H insertion and annulation, and offers the advantages of a broad substrate scope, excellent functional tolerance, and simplicity of operation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Jing Qi, Jinhui Xu, Hwee Ting Ang, Bingbing Wang, Nipun Kumar Gupta, Srinivas Reddy Dubbaka, Patrick O'Neill, Xianwen Mao, Yanwei Lum, Jie Wu
Summary: In this study, a novel electrophotochemical approach is presented for the selective trifluoromethylation of (hetero)-arenes using trifluoroacetic acid (TFA) as the CF3 source. The method offers sustainable and environmentally-friendly synthesis of CF3-, CF2H-, and perfluoroalkyl-containing (hetero)-arenes with improved chemoselectivity by light irradiation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Xuan Zhan, Zakir Ullah, Donghyeon Kim, Bilal Mustafa, Hyungwook Kwon, David G. Churchill, Zeev Gross
Summary: The effect of multi-CF3 substitution in porphyrinoids was investigated through a combination of experiments and calculations. Six compounds with bis-trifluoromethylated tpfc structures were prepared via two different reaction pathways, and the photocatalytic trifluoromethylation in porphyrin chemistry was achieved for the first time. The structural assignments of these compounds were successfully achieved, and their photophysical and electrochemical properties were analyzed and correlated with TDDFT energy level analyses.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Ning Chen, Song-Lin Zhang
Summary: A selective intermolecular amino-trifluoromethylation of alkenes has been developed, which can produce a range of biologically active beta-trifluoromethyl amines. This method utilizes a high-valent Cu(III)-CF3 complex to generate the CF3 radical and Cu(II) oxidant through homolytic bond cleavage. This unique method simplifies the reaction conditions, enhances operational convenience, and suppresses various side reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Kingshuk Mahanty, Suman Kumar Saha, Atreyee Halder, Suman De Sarkar
Summary: The developed methodology presents an eco-friendly approach for electro-oxidative CF3-radical generation, leading to the synthesis of a beta,gamma-unsaturated oxime and subsequent cascade cyclization to form an isoxazoline scaffold. This method offers mild, robust, and scalable reaction conditions and has a wide range of substrate applicability. Mechanistic studies demonstrate the importance of anodic oxidation for the cascade process. Further conversion of the isoxazoline provides valuable derivatives.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Jian Li, Yang Liu, Zebin Chen, Jiaming Li, Xiaoliang Ji, Lu Chen, Yubing Huang, Qiang Liu, Yibiao Li
Summary: A method for obtaining substituted thiophenes with functional potential through metal-free dehydration and sulfur cyclization was described. The reaction of alkynols with elemental sulfur (S-8) or EtOCS2K yielded moderate-to-good yields. The method showcased the base-free generation of a trisulfur radical anion (S-3(center dot-)) and its addition to alkynes as an initiator. This research broadens the applications of S-3(center dot-) in the synthesis of sulfur-containing heterocycles.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Canlin Zou, Hongting Wu, Jiangtao He, Yunfei Hu, Weijie Deng, Xinling Li, Jinhui Hu, Yibiao Li, Yubing Huang
Summary: An efficient anodic C(sp(3))-H acyloxylation protocol has been developed, which enables the direct oxidation of indolin-3-ones to obtain various C2-acyloxy indolin-3-ones without the need for metal catalysts and external oxidants. The practicality of this protocol has been demonstrated through the effective application of several medical drugs and gram-scale experiments.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Jian Li, Jiaming Li, Runfa He, Jiasheng Liu, Yang Liu, Lu Chen, Yubing Huang, Yibiao Li
Summary: A concise and efficient protocol was developed to obtain diverse substituted pyridines and pyrimidines with high selectivity. The reaction involves metal-free cascade annulation of isopropene derivatives. By using isopropene derivatives as C3 synthons, NH4I as the N source, and formaldehyde or dimethyl sulfoxide as the carbon source, this reaction efficiently forms intermolecular C-N and C-C bonds.
Article
Chemistry, Organic
Hongting Wu, Weihao Chen, Weijie Deng, Ling Yang, Xinling Li, Yunfei Hu, Yibiao Li, Lu Chen, Yubing Huang
Summary: A regioselective coupling of aliphatic ketones with alkenes has been achieved through cathodic reduction, leading to the synthesis of diverse tertiary alcohols with substrate-dependent regioselectivity.
Article
Chemistry, Organic
Runfa He, Yang Liu, Yingqi Feng, Lu Chen, Yubing Huang, Feng Xie, Yibiao Li
Summary: A concise and efficient protocol is described for the synthesis of a series of substituted thienopyridine and thienoquinoline derivatives with high selectivity.
Article
Chemistry, Organic
Xiaoliang Ji, Jinli Nie, Xin Peng, Jinhui Hu, Xuetao Xu, Yubing Huang, Yibiao Li, Huanfeng Jiang
Summary: Here, we have developed a new Pd-catalyzed reaction for the synthesis of dihaloalkenyne derivatives. This reaction proceeds under mild conditions with high selectivity and functional group tolerance.
Article
Chemistry, Organic
Hongting Wu, Xinling Li, Ling Yang, Weihao Chen, Canlin Zou, Weijie Deng, Ziliang Wang, Jinhui Hu, Yibiao Li, Yubing Huang
Summary: An efficient and safe cathodic carbonyl alkylation reaction has been achieved using iron as an electrochemical activated catalyst. The reaction forms intermolecular C-C bonds between unactivated alkyl halides and aryl ketones or aldehydes, producing a variety of tertiary or secondary alcohols.
Article
Chemistry, Multidisciplinary
Xiaoliang Ji, Xin Peng, Huanliang Hong, Yanghao Xu, Jinli Nie, Lu Chen, Zongwen Mo, Yibiao Li, Huanfeng Jiang
Summary: Herein, a Pd-II-catalyzed method for the construction of functionalized dihaloalkenynes from haloalkynes via self-haloalkynylation reaction is reported. The method eliminates the need for specialized ligands or oxidizing additives and is tolerant of a wide range of haloalkynes, including those with electron-donating and electron-withdrawing functional groups. By using an opposite lithium halide to the starting haloalkyne, high regio- and stereoselectivity can be achieved, yielding the desired 1-bromo-2-chloroalkenyne or 2-bromo-1-chloroalkenyne products.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Lu Chen, Ya Li, Xiaoyan Bai, Dian Dong, Meiwei Pan, Ling Huang, Runqin Huang, Xiaotong Long, Yibiao Li
Summary: A novel method for the divergent and regioselective synthesis of (E)-2-bromo-1-phenylvinyl trifluoromethanesulfonates is proposed by using readily available alkynes, N-bromosuccinimide (NBS), and trimethylsilyl trifluoromethanesulfonate (TMSOTf) catalyzed by ruthenium(III) acetate [Ru(OAc)(3)]. This method provides a fundamental basis for the development of advanced functional compounds, including drugs and organic functional materials, as it can tolerate a wide range of functional groups. The potential value of this new reaction in organic synthesis is demonstrated by the use of alkynes derived from bioactive molecules such as l(-)-borneol.
Article
Chemistry, Multidisciplinary
Yang Liu, Yingqi Feng, Jinli Nie, Sijie Xie, Xin Pen, Huanliang Hong, Xiuwen Chen, Lu Chen, Yibiao Li
Summary: In this study, the diversity-oriented aromatization of cyclic hydrocarbons was achieved through the potassium ethyl xanthogenate (EtOCS2K)/NH4I-mediated methylthiyl radical addition and thioether elimination reaction under transition-metal-free conditions.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Lu Chen, Zhenyuan Lin, Zilong Zhang, Xiaoyan Bai, Huahui Wang, Ya Li, Hao Lu, Wei Yang, Huanying Li, Yibiao Li
Summary: Carbonyl compounds are crucial in organic synthesis due to their versatile reactivities, but current transformations have limitations. Developing a novel MOFsTiO2 photocatalyst for converting carbonyl compounds to acetals/ketals is critical. This strategy demonstrates efficient acetalisations of carbonyl compounds, providing access to a wide variety of compounds with excellent yields and broad substrate scope, making it applicable in green catalytic systems.
JOURNAL OF CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Weijie Deng, Yunfei Hu, Jinhui Hu, Xinling Li, Yibiao Li, Yubing Huang
Summary: A metal-free electrochemically induced strategy has been developed for the regioselective hydro/deuterophosphonylation of electron-rich alkenes with P(O)H compounds, providing various Markovnikov-type adducts in high yields. Monodeuterated organophosphorus compounds with high deuterium incorporation can be obtained by adding D2O as the D source. The protocol offers broad substrate scope, low energy consumption, high atom economy, and scalability.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Chuyuan Lin, Lu Chen, Huaping Lin, Yibiao Li, Chengshuo Shen, Min Zhang
Summary: In this study, we present a new and practical approach for synthesizing aryl α,α-chlorofluoro arylketones directly in aqueous trifluoroethanol using a compatible system of selectfluor and NaCl. The method is metal-free and utilizes readily available feedstocks, demonstrating good tolerance towards functional groups. This work provides a raw material basis for the further preparation of fluorinated organic molecules.
ORGANIC CHEMISTRY FRONTIERS
(2022)
