Article
Chemistry, Multidisciplinary
Wen-Hao Li, Bo-Chao Ye, Jiarui Yang, Ye Wang, Chang-Jie Yang, Ying-Ming Pan, Hai-Tao Tang, Dingsheng Wang, Yadong Li
Summary: This paper presents a single-atom catalyst (SAC) strategy to improve the cobalt-catalysed fluorination of acyl chlorides. The stable Co-F intermediate formed by oxidative fluorination of Co-1-N-4@NC SAC can replace the unstable high-valent cobalt catalytic system and avoid the use of phosphine ligands. This work demonstrates the potential of inorganic SACs in organofluorine chemistry and provides a valuable reference for studying the structure-activity relationship in catalyst design and chemical reaction mechanisms.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Inorganic & Nuclear
Tien Tan Bui, Wan Pyo Hong, Hee-Kwon Kim
Summary: The fluorine motif is a crucial structure in organic and medicinal chemistry, widely used in pharmaceuticals. Visible light-mediated reactions have recently emerged as a valuable synthetic strategy, with various photochemical fluorination methods being utilized to produce a wide range of fluorinated products.
JOURNAL OF FLUORINE CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Muqing Chen, Yaoxiao Zhao, Fei Jin, Mengyang Li, Runnan Guan, Jinpeng Xin, Yang-Rong Yao, Xiang Zhao, Guan-Wu Wang, Qianyan Zhang, Su-Yuan Xie, Shangfeng Yang
Summary: This study reports the first chemical functionalization of an emerging endohedral clusterfullerene mu(3)-CCF. The high regioselectivity of the reaction is determined by the presence of Ti(IV) ion. A similar reaction involving a Ti(III)-containing nitride clusterfullerene reveals the peculiarity of mu(3)-CCF's chemical property due to the non-rare earth metal Ti with a high oxidation state.
INORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Physical
Yao Luo, Qi Wei, Liangkun Yang, Yuqiao Zhou, Weidi Cao, Zhishan Su, Xiaohua Liu, Xiaoming Feng
Summary: The synthesis of chiral ketones has been a significant focus in chemistry research. In this study, researchers successfully achieved a highly selective radical hydroacylation reaction for α-substituted α,β-unsaturated carbonyl compounds using anthraquinone photocatalyst and chiral N,N'-dioxide/metal complexes. This method provides a mild and robust approach to access a wide range of chiral ketones with α-tertiary stereocenters.
Article
Chemistry, Applied
Liangying Wu, Yang Song, Zhanchong Li, Jiabao Guo, Xiaoquan Yao
Summary: A new method for generating fluoroalkylated arylamines under mild conditions with a wide substrate scope and excellent yields was developed using copper(II)-catalysed aerobic oxidative coupling. Preliminary studies suggest the reaction occurs via a radical mechanism, and the protocol offers an alternative green route for constructing fluorinated compounds by using atmospheric O2 as an oxidant.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Review
Chemistry, Multidisciplinary
Nayanthara Asok, Joshua R. Gaffen, Thomas Baumgartner
Summary: Recent advances in synthetic chemistry have led to the transformation of main-group molecules into powerful materials with a wide range of applications. Electron-deficient materials have been particularly targeted due to their limited availability and stability. Understanding their electronic and molecular interactions is crucial to expand their utility. Incorporating electron-deficient main-group elements, such as boron, into organic frameworks was considered effective, but challenging conditions have led to the exploration of other elements. Heavy main-group elements like Si, Ge, P, As, Sb, Bi, S, Se, and Te are advantageous for electron-accepting materials. Organophosphorus species, especially phosphole, have unique properties and are extensively studied in materials chemistry research. They have outstanding electronic, chemical, and structural properties, making them suitable for various applications.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Physical
Chengcheng Dong, Linzhu Cao, Xinmeng Xu, Xin Tao, Guangshan Zhu
Summary: This article presents a facile synthesis method for Lewis acidic boron-containing porous organic polymers (B-POPs) via hydroboration polymerization reaction. The method has high atom economy and results in porous alkenyl borane polymers (PABPs) with high boron content and strong Lewis acidity.
Article
Chemistry, Physical
Cuncai Lv, Pingping Lou, Jiarong Chang, Ruining Wang, Linjie Gao, Yaguang Li
Summary: The MCH-toluene-hydrogen cycle has potential in industrial applications for recycling matter and energy. A hybrid catalyst of single-atom nickel anchored on cerium oxide nanosheets has been successfully constructed, demonstrating excellent thermal catalytic activity in MCH dehydrogenation. By combining this catalyst with a solar-to-heat device, a solar-heating catalysis mode has been developed for scalable MCH dehydrogenation under solar irradiation.
JOURNAL OF POWER SOURCES
(2023)
Review
Chemistry, Organic
Hariharaputhiran Subramanian, Mukund P. Sibi
Summary: Hydrogen atom transfer (HAT) is an important class of radical reactions. Despite extensive research, controlling the stereoselectivity of the HAT process remains challenging. This review highlights the use of small molecule chiral HAT reagents and catalysts to achieve stereoselectivity in free radical reactions, as well as the recent advancements in photoenzymatic catalysis for efficient HAT reactions.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Multidisciplinary Sciences
Isabelle Nathalie-Marie Leibler, Makeda A. Tekle-Smith, Abigail G. Doyle
Summary: The study introduces a novel method using nucleophilic coupling partners through successive hydrogen atom transfer and oxidative radical-polar crossover. This strategy transforms C(sp(3))-H bonds into carbocations, enabling diverse bond formations with various nucleophiles and providing new site-selectivity for late-stage C(sp(3))-H functionalization.
NATURE COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Lu Lin, Jun Zhu
Summary: Aromaticity is an important concept in chemistry, and enhancing it can bring thermodynamic stability to compounds. This study found that the stronger the antiaromaticity of heterocyclics, the higher the thermodynamic stability of the corresponding radicals, which is contrary to the general understanding of aromaticity enhancing stability. Strong pi-bonding between heterocyclics and alpha-methyl carbon was identified as a factor for improving the thermodynamic stability of radicals.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Haiyu Zhou, Tongtong Bai, Yanlin Pan, Yongliang Wei, Tongdao Wang
Summary: The study describes the synthesis and characterization of air-stable heterobimetallic Os-Ag hydrides, providing a new route for constructing stable heterobimetallic complexes. The complexes are neutral and feature organo-metallic bidentate cheating ligands coordinating with the AgPPh3 cation, enhancing their stability.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Sebastian A. Schwengers, Chandra Kanta De, Oleg Grossmann, Joyce A. A. Grimm, Natascha R. Sadlowski, Gabriela G. Gerosa, Benjamin List
Summary: A single-flask synthesis method for efficient Bronsted acids was developed, allowing for the rapid production of imidodiphosphate-based compounds. The catalysts exhibit high structural confinement and a wide acidity range, with one catalyst showing highly enantioselective sulfoxidation activity. Additionally, a novel super acidic catalyst motif, IDPii, was discovered, demonstrating extreme reactivity in the alpha-methylation reaction of a silyl ketene acetal with methanol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Tobias E. Schirmer, Alessa B. Rolka, Tobias A. Karl, Ferdinand Holzhausen, Burkhard Koenig
Summary: A broadly applicable method for trifluorome-thylthiolation of various types of C-H bonds using decatungstate anion as the sole catalyst has been developed, achieving good regioselectivities in 40 examples, including natural product derivatization. Additionally, SCF3-drug analogues were synthesized by subsequent functionalization of the SCF3 products, highlighting the importance of this photocatalyzed C-H functionalization.
Article
Chemistry, Physical
Huaifeng Li, Daniel Lupp, Pradip K. Das, Li Yang, Theo P. Goncalves, Mei-Hui Huang, Marwa El Hajoui, Lan-Chang Liang, Kuo-Wei Huang
Summary: The new imination methodology with a base-metal nickel PN3 pincer catalyst features one-step, waste-free, and high atom-economical characteristics, avoiding the difficulties in purification and waste disposal in traditional methods. Mechanistic insight reveals a non-metal-ligand cooperation pathway, providing an important theoretical basis for modern organic synthesis.
Article
Chemistry, Medicinal
Yuji Sumii, Kentaro Kamiya, Takehiko Nakamura, Kenta Tanaka, Takumi Kaji, Junya Mukomura, Naoyuki Kotoku, Masayoshi Arai
Summary: The current treatment for tuberculosis is long and complex due to the ability of Mycobacterium tuberculosis to enter a dormant state. Identifying new compounds with different chemical structures is essential for improving treatment outcomes. This study investigates the structure-activity relationship of a potential anti-tuberculosis compound and successfully develops a probe molecule for detecting its target protein.
Article
Multidisciplinary Sciences
Satoshi Yamanaka, Yuto Horiuchi, Saya Matsuoka, Kohki Kido, Kohei Nishino, Mayaka Maeno, Norio Shibata, Hidetaka Kosako, Tatsuya Sawasaki
Summary: This article introduces a method based on AirID to identify drug-induced neo-substrates through proximity-dependent biotinylation. The study identifies several new CRBN substrates and demonstrates that this method can serve as a general strategy for studying drug-induced protein-protein interactions in cells.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hiroto Uno, Koki Kawai, Taichi Araki, Motoo Shiro, Norio Shibata
Summary: Gem-difluoromethylene moieties are attractive in medicinal chemistry due to their ability to mimic other more ubiquitous functional groups. A novel asymmetric method for their construction was developed, allowing easy access to chiral 1,3-dioxanes that contain a tetrasubstituted difluoroalkyl stereogenic center. The gem-difluoro substitution pattern promotes the reaction, and various substrates were suitable for this method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Kentaro Iwaki, Koki Maruno, Osamu Nagata, Norio Shibata
Summary: The trans-tetrafluoro-lambda 6-sulfanyl (SF4) unit is of medicinal interest due to its high electronegativity, lipophilicity, and unique hypervalent structure. Despite the difficulties in synthesis, the first synthesis of (ethynyl-trans-tetrafluoro-lambda 6-sulfanyl) pyridines and their use as versatile reagents for SF4-alkynylation to carbonyl compounds was reported. The addition reaction of t-ethynyl-SF4-pyridines to carbonyl groups in the presence of MeLi yielded pyridine-SF4-propargylic tertiary and secondary alcohols in high yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Kentaro Iwaki, Kazuhiro Tanagawa, Soichiro Mori, Koki Maruno, Yuji Sumii, Osamu Nagata, Norio Shibata
Summary: In this study, we reported a metal-free hydration reaction of pyridine-SF4-alkynes under acidic conditions, which synthesized pyridine-SF4-methyl ketones with yields ranging from 59% to 93%. We further demonstrated the synthetic applications of these compounds, including chlorination, NaBH4 reduction, Baeyer-Villiger oxidation, and the generation of enol triflates. These compounds show promise as useful building blocks in the synthesis of a wide range of SF4-containing drug candidates.
Article
Chemistry, Organic
Koki Maruno, Kenshiro Hada, Yuji Sumii, Osamu Nagata, Norio Shibata
Summary: In this study, pyridine-SF4-isoxazolines were synthesized via the regioselective 1,3-dipolar cycloaddition reaction. The SF4 linker, connecting two heterocycles, was found to be a potential alternative in drug design.
Article
Chemistry, Multidisciplinary
Yamato Fujihira, Hiroto Iwasaki, Yuji Sumii, Hiroaki Adachi, Takumi Kagawa, Norio Shibata
Summary: This article describes a method for the chemical transformation of two HFCs, which can synthesize important pharmaceutical and agrochemical compounds. The method effectively utilizes HFCs, making it attractive for industrial use and an alternative to current HFC decomposition processes.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Physical
Masahiro Sugiura, Kazuki Ishikawa, Kota Katayama, Yuji Sumii, Rei Abe-Yoshizumi, Satoshi P. Tsunoda, Yuji Furutani, Norio Shibata, Leonid S. Brown, Hideki Kandori
Summary: This study reports a novel photochemical reaction mediated by a microbial rhodopsin, leading to the selective transition from the all-trans to 7-cis form.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
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.
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)
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
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
Chemistry, Multidisciplinary
Xuemei Liu, Chaonan Cui, Shuoshuo Wei, Jinyu Han, Xinli Zhu, Qingfeng Ge, Hua Wang
Summary: This study presents a new strategy for designing efficient photocatalysts that can convert CO2 into hydrocarbons by utilizing synergistic catalytic sites. The findings provide a solution for the selective photocatalytic reduction of CO2 to CH4.
Article
Chemistry, Multidisciplinary
Chengxian Hu, Dan Wang, Lu Wang, Ying Fu, Zhengyin Du
Summary: A novel one-pot, three-component reaction conducted under electrochemical conditions was studied. The reaction involved 2-aminothiophenols, aldehydes, and malononitrile, using TBABF4 as an electrolyte and CuI as a catalyst. The proposed reaction mechanism suggested that CuI served as an electron relay. This method offers simplified operation, high atom economy, and mild reaction conditions.
Article
Chemistry, Multidisciplinary
Zhi Yang, Yu Chen, Linxi Wan, Yuxiao Li, Dan Chen, Jianlin Tao, Pei Tang, Fen-Er Chen
Summary: A highly enantioselective method for the complete hydrogenation of pyrimidinium salts using Ir/(S,S)-f-Binaphane complex as the catalyst was developed. This method provides easy access to fully saturated chiral hexahydropyrimidines, which are prevalent in many bioactive molecules. The reactions exhibit high yields and enantioselectivities under mild reaction conditions without additives. Successful application of this methodology in a continuous flow fashion further extends its practical utility.
Article
Chemistry, Multidisciplinary
Tina Jeoh, Jennifer Danger Nill, Wujun Zhao, Sankar Raju Narayanasamy, Liang Chen, Hoi-Ying N. Holman
Summary: In this study, the enzymatic hydrolysis of cellulose was investigated using real-time infrared spectromicroscopy. The spatial heterogeneity of cellulose was found to impact the hydrolysis kinetics. Hydration affected cellulose ordering, and Cel7A preferentially removed less extensively hydrogen bonded cellulose.
Article
Chemistry, Multidisciplinary
Tiphaine Richard, Walid Abdallah, Xavier Trivelli, Mathieu Sauthier, Clement Dumont
Summary: An effective method of grafting functionalities onto lignin based on glycerol carbonate has been developed using an efficient nickel-catalysed telomerisation reaction. This method allows lignin to have new reactive functions and reduces the glass transition temperatures of modified lignins, thereby expanding the application range of lignin-based resins.
Article
Chemistry, Multidisciplinary
Jing Qi, Xiyan Wang, Gan Wang, Srinivas Reddy Dubbaka, Patrick ONeill, Hwee Ting Ang, Jie Wu
Summary: This study presents a green and environmentally friendly approach for the synthesis of imides using electrocatalytic oxidation with H2O as the oxygen source. The method eliminates the need for toxic or expensive oxidants and achieves high yields under mild reaction conditions. It shows broad substrate compatibility and potential for industrial applications.
Article
Chemistry, Multidisciplinary
Babasaheb Sopan Gore, Lin-Wei Pan, Jun-Hao Lin, Yi-Chi Luo, Jeh-Jeng Wang
Summary: Here, we report a visible light-promoted intramolecular radical cascade reaction for the construction of fluorenol and naphthalene-fused cyclopropyl carbaldehyde derivatives. This method offers mild reaction conditions, a broad substrate scope, excellent step efficiency, and scalability, without the need for external chemical oxidants. The novelty of this protocol was demonstrated by synthesizing chrysene analogs and performing late-stage functionalizations.
Article
Chemistry, Multidisciplinary
Juho Antti Sirvio, Idamaria Romakkaniemi, Juha Ahola, Svitlana Filonenko, Juha P. Heiskanen, Ari Ammala
Summary: This article discusses the method of using supramolecular interaction between an aromatic hydrogen bond donor and lignin to achieve rapid delignification of softwood at low temperatures.
Article
Chemistry, Multidisciplinary
Yunyan Meng, Chunxiang Pan, Na Liu, Hongjiang Li, Zixiu Liu, Yao Deng, Zixiang Wei, Jianbin Xu, Baomin Fan
Summary: A novel visible light-driven synthesis method for 2,3-diamines has been developed, which has mild conditions, avoids the use of metal reagents, and can synthesize diamines and diols in one pot.
Article
Chemistry, Multidisciplinary
Mingqing Huang, Haiyang Huang, Mengyao You, Xinxin Zhang, Longgen Sun, Chao Chen, Zhichao Mei, Ruchun Yang, Qiang Xiao
Summary: A direct air-oxidized strategy for the synthesis of benzo[b]phosphole oxides was developed in this study. Arylphosphine oxides were transformed into phosphinoyl radicals, which were further combined with various alkynes to achieve the desired products. DFT calculations revealed the mechanism of phosphinoyl radical formation.
Article
Chemistry, Multidisciplinary
Anwei Wang, Jiayin Huang, Chunsheng Zhao, Yu Fan, Junfeng Qian, Qun Chen, Mingyang He, Weiyou Zhou
Summary: This study demonstrates an innovative strategy for the aerobic oxidation of C(sp(3))-H bonds using gamma-valerolactone. By optimizing the reaction conditions and utilizing specific catalysts, efficient oxidation of C(sp(3))-H bonds is achieved with good chemoselectivity in certain cases.
Article
Chemistry, Multidisciplinary
Shun Li, Likai Tong, Zhijian Peng, Bo Zhang, Xiuli Fu
Summary: Sulfide compounds show promise as electrocatalysts for water splitting, but their performance is limited by factors such as limited active sites and hindered substance transport. This study successfully prepared a high-entropy sulfide (ZnCoMnFeAlMg)(9)S-8, which reduced grain size and increased specific surface area, enabling the realization of a dual-functional catalyst with multiple catalytic sites. High entropy also modulated the electronic properties of sulfides, reducing the potential energy barrier for hydrolysis. This research introduces a new approach for functionalizing high entropy nanomaterials and improves the performance of water splitting catalysts.
