Article
Chemistry, Organic
Shuya Xing, Cheng Ma, Wen Liu, Shao-Fei Ni, Dianhu Zhu, Li-Wen Xu, Xinxin Shao
Summary: A novel strategy for Lewis base-activated trifluoromethylsulfinylation of allylic alcohols is demonstrated. Controllable synthesis of structurally varied allylic trifluoromethanesulfones and trifluoromethanesulfinate esters was achieved. This metal-free, catalytic divergent transformation features good functional group tolerance and late-stage modification of bioactive molecules. Mechanistic studies revealed interaction between Lewis bases and N-(trifluoromethylsulfinyl)phthalimide, generating an ion pair adduct followed by O-trifluoromethylsulfinylation with allylic alcohols.
Article
Chemistry, Organic
Changge Zheng, Chao Jiang, Shuai Huang, Kui Zhao, Yingying Fu, Mingyu Ma, Jianquan Hong
Summary: This reaction offers an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. It has the potential to be an alternative to the current industrial production method due to easy substrates, excellent functional group compatibility, and operational simplicity.
Article
Chemistry, Organic
Junqing Liang, Wen Fu, Lefeng Dong, Cong Zhou, Qinglong Yuan, Wenning Chang, Wu-Lin Yang, Xiaoyong Xu, Xusheng Shao, Zhong Li
Summary: In this study, novel electrophilic N-difluoromethylthiophthalimide reagents were designed and easily synthesized using commercially available and economical chemicals. These reagents selectively reacted with various nucleophiles, including Grignard reagents, boronic acids, β-ketoesters, and anilines, to produce structurally diverse α-difluoromethylthiolated ketones in high yields. The successful formal synthesis of active antifungal compounds further confirmed the practicality of these reagents.
Article
Chemistry, Organic
Xuemin Li, Fengxia Sun, Haofeng Shi, Beibei Zhang, Jiaxin He, Jialiang Wu, Yunfei Du
Summary: The BnSRf (R-f = CF2H or CF3)/mCPBA/Tf2O system is an effective multicomponent reagent system for the one-pot synthesis of di/trifluoromethylthiolated heterocycles from alkynes. The reaction proceeds through a cascade sequence involving oxidation of BnSRf by mCPBA, activation of in situ-generated sulfoxide by Tf2O, and intramolecular cyclization/fluoromethylthiolation of the alkyne substrates enabled by the formed electrophilic sulfonium salt to give di/trifluoromethylthiolated heterocycles.
Article
Chemistry, Organic
Haofeng Shi, Xingzong Wang, Xiaoxian Li, Beibei Zhang, Xuemin Li, Jingran Zhang, Jingyue Yang, Yunfei Du
Summary: In this study, the combined use of BnS(O)CF3/BnSe(O)CF3 with Tf2O was employed to achieve the efficient synthesis of 4-(trifluoromethylthio/ trifluoromethylseleno)isocoumarins from 2-alkynylbenzoates, which is of significance in biological research. The mechanistic pathway was proposed to involve interrupted Pummerer reactions followed by a concerted trifluoromethylthiolation/selenolation and lactonization process.
Article
Chemistry, Organic
Ankita Thakur, Shiv Shankar Gupta, Ankit Kumar Dhiman, Upendra Sharma
Summary: A photocatalytic approach has been used to introduce a trifluoroethanol unit onto isoquinolines by employing N-trifluoroethoxyphthalimide as a hydroxyfluoroalkyl radical precursor. The involvement of a free-radical pathway was confirmed by radical quenching experiments, and DFT calculations supported the intramolecular 1,2-HAT reactivity of the trifluoroethoxy radical with the trifluoroethanol radical. Fluorescence quenching studies revealed that isoquinoline was responsible for the quenching of Ir photocatalyst emission. A catalytic cycle involving the reaction of trifluoroethanol radical with isoquinolines was proposed.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Yan-mei Li, Jin-feng Fu, Long-qiang He, Wei-na Li, Esmail Vessally
Summary: Trifluoromethylthiolative difunctionalization of alkenes is an important and hot research area that provides an ideal strategy for the preparation of alkyl trifluoromethyl sulfides.
Article
Chemistry, Organic
Yangjie Huang, Mengjia Zhang, Qi Lin, Zhiqiang Weng
Summary: The article summarizes recent work on direct introduction of the SCF (3) group using [(bpy)CuSCF3] as a trifluoromethylthiolating reagent. Efficient strategies for synthesizing trifluoromethylthiolated compounds, including aryl, alkenyl, and alkyl halides, and arylboronic acids, have been disclosed. These reactions yield various trifluoromethyl sulfides in good yields.
Article
Chemistry, Multidisciplinary
Wen-Qi Xu, Xiu-Hua Xu, Feng-Ling Qing
Summary: This article describes an unprecedented synthesis of trifluoromethylthiophosphonium salts through Mislow-Evans-type rearrangement. The resulting salts were isolated and characterized. These fluoroalkylphosphonium salts exhibited versatile reactions with nucleophiles and carboxylic acids, as well as successful catalytic hydrotrifluoromethylation and hydrotrifluoromethylthiolation of unactivated alkenes.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Jiang Wu, Qilong Shen
Summary: In recent years, the strategic installation of a fluorine atom or a fluoroalkyl group at specific positions of target molecules has become a routine practice for medicinal chemists in order to fine-tune the structure of lead compounds. The difluoromethylthio group has attracted attention due to its weak acidity, lipophilic nature, and stability, making it a favorable functional group in drug design. Efficient strategies for introducing the difluoromethylthio group into small molecules under mild conditions are urgently needed.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Organic
Ankun Li, Yuxuan Li, Junjie Liu, Jingqi Chen, Kui Lu, Di Qiu, Maurizio Fagnoni, Stefano Protti, Xia Zhao
Summary: This protocol for the synthesis of aryl trifluoromethyl thioethers under visible-light-driven conditions does not require the use of photocatalysts or metal catalysts. It utilizes the unique properties of arylazo sulfones and S-trifluoromethyl arylsulfonothioates as precursors, making the procedure easy to handle.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Xiaoyu Chen, Congcong Pei, Bo Liu, Jingya Li, Dapeng Zou, Yangjie Wu, Yusheng Wu
Summary: This article describes a new method for the construction of potentially medicinally valuable trifluoromethylthio-substituted dioxodibenzothiazepines through the Cu-assisted trifluoromethylthiolation/radical cascade cyclization of alkynes with readily available and stable AgSCF3.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Jinrui Bai, Shijia Li, Dan Qi, Zhuoheng Song, Bin Li, Lin Guo, Lijuan Song, Wujiong Xia
Summary: In this article, a visible-light-induced trifluoromethylsulfonylation reaction of diazo compounds is reported. The developed synthetic method utilizes the coordination of relatively rare trifluoromethyl sulfone radicals to the Mn(acac)(3) catalyst, leading to the formation of alpha-trifluoromethyl sulfone esters in good to moderate yields (up to 82%). The reaction exhibits broad substrate scope and can be easily conducted under mild conditions. Furthermore, the plausible mechanism of the reaction was investigated through DFT calculations.
Article
Chemistry, Organic
Jinrui Bai, Shijia Li, Dan Qi, Zhuoheng Song, Bin Li, Lin Guo, Lijuan Song, Wujiong Xia
Summary: A visible-light-induced trifluoromethylsulfonylation reaction of diazo compounds is presented. The reaction captures relatively rare trifluoromethyl sulfone radicals through coordination to the Mn(acac)3 catalyst, resulting in the synthesis of alpha-trifluoromethyl sulfone esters in good to moderate yields (up to 82%). The protocol demonstrates broad substrate scope and can be conducted under mild reaction conditions. Additionally, a plausible reaction mechanism was investigated through DFT calculations.
Article
Chemistry, Organic
Victor Garcia-Vazquez, Larry Hoteite, Christopher P. Lakeland, David W. Watson, Joseph P. A. Harrity
Summary: This method provides access to analogs of 3-fluoro- and trifluoromethylthio-piperidines with rich functionality, allowing for chemoselective derivatization with high diastereocontrol.
Article
Chemistry, Multidisciplinary
Tao Wang, Yang Zou, Zhongyan Huang, Nengquan Li, Jingsheng Miao, Chuluo Yang
Summary: By modifying the structure of conjugated polymers, narrowband emission properties of delayed fluorescence conjugated polymers have been achieved, providing new insights for the design of high-quality OLED displays.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Optics
Yu Xuan Hu, Jingsheng Miao, Tao Hua, Zhongyan Huang, Yanyu Qi, Yang Zou, Yuntao Qiu, Han Xia, He Liu, Xiaosong Cao, Chuluo Yang
Summary: This study reports a heavy-atom incorporating emitter, BNSeSe, based on a selenium-integrated boron-nitrogen skeleton, which exhibits high photoluminescence quantum yield and fast reverse intersystem crossing rate. By utilizing BNSeSe, green OLEDs demonstrate high operational efficiency and significantly reduced efficiency roll-off at high brightness.
Article
Chemistry, Multidisciplinary
Junjie Wang, Nengquan Li, Cheng Zhong, Jingsheng Miao, Zhongyan Huang, Mingxin Yu, Yu Xuan Hu, Sai Luo, Yang Zou, Kai Li, Chuluo Yang
Summary: A high-performance MR-TADF emitter with high PLQY, short delayed fluorescence lifetime, and high color purity is achieved through coordination of Au with B/N-embedded polycyclic ligand. Vacuum-deposited OLEDs exhibit high-performance electroluminescence and the solution-processed OLED also achieves excellent performance.
ADVANCED MATERIALS
(2023)
Article
Engineering, Environmental
Zhaoran Hao, Nengquan Li, Jingsheng Miao, Zhongyan Huang, Xialei Lv, Xiaosong Cao
Summary: This work describes the first example of circularly polarized thermally activated delayed fluorescent (CP-TADF) materials containing heteroatomic stereocenter. The chiral enantiomers assembled in a specific manner exhibit distinct luminescence signals and highly efficient emission in film state.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Nengquan Li, Zhanxiang Chen, Changjiang Zhou, Fan Ni, Zhongyan Huang, Xiaosong Cao, Chuluo Yang
Summary: This study discovered two new host materials, 3CzAcPy and 9CzAcPy, which have high triplet energy levels, thermal stability, and excellent film morphology for organic light-emitting diodes (OLEDs). The isomeric effect of the host materials has a significant impact on the properties and performance of solution-processed TADF OLEDs. The new hosts achieved state-of-the-art device performance for both donor-acceptor type and multi-resonance TADF emitters.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Norio Shibata, Dominique Cahard
Summary: From 2000, our two research groups independently and simultaneously designed and developed a novel family of electrophilic fluorinating reagents based on the use of Cinchona alkaloids. The chiral N-fluoro ammonium salts demonstrated the highest efficiency compared to prior art in enantioselective electrophilic fluorination for a wide range of substrates. In this account, we tell our respective stories, how the same idea germinated in our laboratories, the characterization of the chiral reagents, the use in stoichiometric quantity then the development of a catalytic version, the application to the synthesis of chiral fluorinated molecules of pharmaceutical interest, and finally the exploitation of our reagents by other teams and for other applications.
Review
Chemistry, Multidisciplinary
Yuji Sumii, Norio Shibata
Summary: The trifluoromethyl group is a crucial component in drugs and polymers, making the development of trifluoromethylation reactions a significant area of research in organic chemistry. Various methods, including nucleophilic and electrophilic approaches, transition-metal catalysis, photocatalysis, and electrolytic reactions have been developed over the years. Microflow versions of these reactions have shown great potential for industrial applications due to their scalability, safety, and time efficiency. This review discusses the current state of microflow trifluoromethylation, focusing on different trifluoromethylation reagents and techniques such as continuous flow, flow photochemical, microfluidic electrochemical reactions, and large-scale microflow reactions.
Article
Chemistry, Multidisciplinary
Zhongyan Huang, Honghui Xie, Jingsheng Miao, Yaxiong Wei, Yang Zou, Tao Hua, Xiaosong Cao, Chuluo Yang
Summary: Multipleresonance thermally activated delayed fluorescence (MR-TADF)emitters with a multichannel reverse intersystem crossing (RISC) pathway were developed using an orthogonal linking strategy. The resulting emitter, CzBN3, showed a 23-fold increase in RISC rate, high photoluminescence quantum yield, and narrow emission spectrum. This design strategy enabled high maximum external quantum efficiency and reduced efficiency roll-off in the device. The state-of-the-art electroluminescent performance validates the superiority of this molecular design strategy.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Letter
Chemistry, Organic
Elsayed M. Mahmoud, Soichiro Mori, Yuji Sumii, Norio Shibata
Summary: The synthesis of acyl fluorides from carboxylic acids is achieved using Selectfluor mediated by elemental sulfur. A wide range of acyl fluorides can be accessed while avoiding the formation of acid anhydrides. F-19 NMR spectra indicate that the reactive species in this deoxyfluorination reaction are the in situ generated S-8-fluoro-sulfonium cation A and neutral S-8-difluoride A'.
Article
Multidisciplinary Sciences
Jun Zhou, Zhengyu Zhao, Norio Shibata
Summary: Defluorinative cross-coupling between amines and organic fluorides is achieved via a silylboronate-mediated strategy. This method enables the room-temperature cross-coupling of C-F and N-H bonds, avoiding the high energy barriers associated with thermally induced S(N)2 or S(N)1 amination. The selective activation of the C-F bond of organic fluorides by silylboronate is a significant advantage of this transformation.
NATURE COMMUNICATIONS
(2023)
Article
Engineering, Environmental
Shuni Wang, Yulin Xu, Jingsheng Miao, Tao Hua, Xiaosong Cao, Nengquan Li, Zhongyan Huang, Chuluo Yang
Summary: In this study, two multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters, CzBN-tDPA and CzBN-mCP, were designed by decorating the well-known emitter of CzBN with different diarylamino moieties. These new emitters showed blue emission with peaks at 465 and 464 nm, narrow full-width at half maximum (FWHM) values of 23 and 21 nm, respectively. Organic light-emitting diodes based on these emitters achieved narrowband blue emission with maximum external quantum efficiencies (EQEmaxs) of nearly 20% and low efficiency roll-offs. Hyperfluorescence devices using these emitters could realize a decent EQEmax up to 30.6%.
CHEMICAL ENGINEERING JOURNAL
(2023)
Editorial Material
Chemistry, Multidisciplinary
Norio Shibata, Dinesh Talwar
Summary: The unique properties and applications of fluorine-containing molecules have had significant impact across different scientific fields, from small to large molecules. This special issue provides a comprehensive overview of the state-of-the-art in fluorine chemistry.
Article
Materials Science, Multidisciplinary
Xingyu Huang, Yulin Xu, Jingsheng Miao, Yan-Yun Jing, Shuni Wang, Zeyuan Ye, Zhongyan Huang, Xiaosong Cao, Chuluo Yang
Summary: In this study, a series of blue TADF emitters were successfully designed and synthesized by incorporating an electron donor into a boron/nitrogen/oxygen ternary doped multiple resonance skeleton. By manipulating the donor strength, a long-range charge transfer triplet state was induced to accelerate the reverse intersystem crossing process while preserving the MR character of the first singlet excited state. The optimized emitter demonstrated deep-blue emission, high photoluminescence quantum yield, and a high RISC rate constant, making it suitable for wide-color-gamut OLED displays.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Jun Zhou, Zhengyu Zhao, Bingyao Jiang, Katsuhiro Yamamoto, Yuji Sumii, Norio Shibata
Summary: In this study, an efficient silylboronate-mediated cross-coupling reaction of aryl fluorides with arylalkanes was developed under transition-metal-free, room-temperature conditions. The method showed good adaptability to aryl fluorides with a C(sp(2))-F bond and can be extended to other coupling partners with a C(sp(3))-H bond. It provides a practical and convenient approach to obtain di- and triarylalkanes with tertiary or quaternary carbon centers.
Article
Materials Science, Multidisciplinary
Yulin Xu, Jianmei Han, Nengquan Li, Zhongyan Huang, Jingsheng Miao, Chuluo Yang
Summary: This study focused on the design and synthesis of two new multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters with high efficiency in electroluminescence devices. The sensitized device based on "TCzBNO" showed excellent performance with a maximum EQE of 36.5% at high brightness.
JOURNAL OF MATERIALS CHEMISTRY C
(2023)
