Article
Chemistry, Multidisciplinary
Jun-Jie Tian, Wei Sun, Rui-Rui Li, Gui-Xiu Tian, Xiao-Chen Wang
Summary: A borane/gold(I) co-catalytic system was designed and applied in C-H functionalization reactions and cycloaddition reactions between tertiary amines and alpha-alkynylenones, efficiently introducing a furan ring into the amine molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Tiffany B. Poynder, Sevan D. Houston, Jason L. Dutton
Summary: The weakly coordinating dianion [B12Cl12](2-) has been utilized in its readily accessible Ag(I) salt form [Ag](2)[B12Cl12] as a catalyst for the chlorination of arenes, alkenes, and alkynes mediated by PhICl2. The promising activity displayed by [Ag](2)[B12Cl12] over various commercially available Ag(I) sources suggests its potential incorporation into commonly used silver catalyst toolkits in organic synthesis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Sripati Jana, Claire Empel, Thanh Vinh Nguyen, Rene M. Koenigs
Summary: The study demonstrates a multiple C-H functionalization reaction of carbazole heterocycles with diazoalkanes using gold catalysts, enabling the introduction of up to six carbene fragments or linking multiple carbazole units into a single molecule. A one-pot stepwise approach allows for the introduction of two different carbene fragments, facilitating orthogonal deprotection and straightforward derivatization.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Subrata K. Ghosh, Mengnan Hu, Robert J. Comito
Summary: The method describes a mild and selective protocol for preparing primary and secondary aliphatic amines in a single pot based on intermolecular sp(3) C-H imination. It constitutes a selective method for complex amine synthesis and a new mechanistic platform for C-H amination. This work demonstrates useful site selectivity within substrates bearing multiple sp(3) C-H bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Chemistry, Organic
Irina A. Mironova, Stefan F. Kirsch, Viktor V. Zhdankin, Akira Yoshimura, Mekhman S. Yusubov
Summary: This review summarizes recent approaches to the direct synthesis of organic azides using hypervalent iodine reagents. The first part discusses the use of unstable azidoiodinanes generated in situ, while the second part focuses on the application of stable azidobenziodoxoles as azidating reagents. The use of azidobenziodoxoles allows for selective direct azidation of specific bonds under mild reaction conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Correction
Chemistry, Organic
Mu-Xue He, Yan Yao, Chun-Zhi Ai, Zu-Yu Mo, Yu-Zheng Wu, Qi Zhou, Ying-Ming Pan, Hai-Tao Tang
Summary: This paper examines the electrochemically-mediated C-H functionalization method for constructing tetrasubstituted furan compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Suvam Bhattacharjee, Sudip Laru, Alakananda Hajra
Summary: A new, efficient, and metal-free protocol has been developed for the remote difunctionalization of unreactive C-H bonds at the benzene core of 2H-indazole by using Koser's reagents as sulfonyloxylating and iodinating agents. This methodology provides easy access to C-4-sulfonyloxylated and C-7-iodinated 2H-indazole derivatives with high regioselectivity, wide functional group tolerance, and broad substrate scope in good to excellent yields, leading to the formation of 4,7 disubstituted 2H-indazoles which serve as precursors for various C-4,7-functionalized 2H-indazoles through simple transformations.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Samata E. Shetgaonkar, Aleena Raju, Hideyasu China, Naoko Takenaga, Toshifumi Dohi, Fateh V. Singh
Summary: Transition metal-catalyzed direct oxidative coupling reactions via C-H bond activation have become a convenient strategy for constructing complex molecules in organic synthesis. By directly transforming C-H bonds into carbon-carbon and carbon-heteroatom bonds, these reactions offer a more efficient alternative to traditional cross-coupling reactions. Hypervalent iodine compounds, with their excellent oxidizing nature and versatile reactivity, have emerged as mainstream reagents in this field.
FRONTIERS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Alexandria N. Leveille, Radell Echemendia, Anita E. Mattson, Antonio C. B. Burtoloso
Summary: The study reported the first example of organocatalytic enantioselective C-H insertion reactions of indoles and sulfoxonium ylides, achieving levels of enantiocontrol in the range of 20-93% ee and moderate yields (up to 50%) under phosphoric acid catalysis. It was found that no nitrogen protection on the indole is necessary for these reactions.
Article
Chemistry, Applied
Jie Ren, Liu Yang, Chao Pi, Xiuling Cui, Yangjie Wu
Summary: In this study, a rhodium(III)-catalyzed divergent C-H bond functionalization of N-aryl amidines with iodonium ylides was described. Carbazolones and zwitterionic salts were synthesized through intermolecular annulation and intramolecular proton transfer under different reaction conditions. This protocol is simple to perform and can tolerate a variety of functional groups, making it practically useful for post-modification of pharmaceutical molecules.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Multidisciplinary
Avishek Das, Nitin T. Patil
Summary: Transition metal-catalyzed enantioselective functionalization of ubiquitous C-H bonds, especially gold-catalyzed processes, has made significant advances in recent years. This review critically highlights the major discoveries and mechanistic insights in this field.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Applied
Bethan Winterson, Dhananjay Bhattacherjee, Thomas Wirth
Summary: The electrochemical synthesis of hypervalent iodine reagents is a rapidly developing field, with numerous reaction types established in the past 5 years, including fluorinations, oxidative cyclizations, C-N and C-H couplings, and oxidations. Electrochemistry provides sustainability benefits by eliminating the need for chemical oxidants, leading to cleaner processes with reduced by-product waste. Recent significant breakthroughs include the first asymmetric application, electrocatalytic applications, and the synthesis of bromine(III) reagents using similar methodologies.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Applied
Myriam Mikhael, Wentao Guo, Dean J. Tantillo, Sarah E. Wengryniuk
Summary: This study presents a method for intramolecular arene C-H etherification via an umpoled alcohol cyclization mediated by an I(III) N-HVI reagent, providing access to functionalized chromane scaffolds from primary, secondary and tertiary alcohols. Computational studies suggest initial formation of an umpoled O-intermediate followed by competitive direct and spirocyclization/1,2-shift pathways.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Physical
Xue-Ya Gou, Yuke Li, Yu-Yong Luan, Wei-Yu Shi, Cui-Tian Wang, Yang An, Bo-Sheng Zhang, Yong-Min Liang
Summary: This study reports the combination of free radical cyclization and ruthenium-catalyzed meta-selective C-H functionalization for the synthesis of arylpyrrolidone derivatives, demonstrating high meta-site selectivity and wide applicability.
Review
Chemistry, Multidisciplinary
Emmanuelle M. D. Allouche, Elija Grinhagena, Jerome Waser
Summary: Hypervalent iodine compounds are powerful reagents for biomolecule functionalization, with recent advances in peptide and protein modification up to June 2021. Their use as group transfer or oxidizing reagents targeting polar, aromatic, or aliphatic amino acids and peptide termini is discussed in this Minireview.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
Xue Liang Li, Shaozhuan Huang, Dong Yan, Jian Zhang, Daliang Fang, Yew Von Lim, Ye Wang, Tian Chen Li, Yifan Li, Lu Guo, Hui Ying Yang
Summary: In this study, a 3D lithiophilic rGO-Ag-S-CNT composite with interlayer-bridged structure was proposed to guide uniform and stable Li plating/stripping. The composite exhibited lower overpotential, higher Coulombic efficiency, and superior long cycling performance compared to other anode materials.
ENERGY & ENVIRONMENTAL MATERIALS
(2023)
Article
Chemistry, Organic
Raphael Simonet-Davin, Jerome Waser
Summary: In this short review, applications of hypervalent iodine reagents for the azidation of organic compounds were described, with a focus on stable cyclic reagents. Important advances in the azidation of C-H bonds, alkenes, and other transformations were highlighted through selected key reports.
SYNTHESIS-STUTTGART
(2023)
Review
Chemistry, Multidisciplinary
Eliott Le Du, Jerome Waser
Summary: Although small, alkynes are highly versatile building blocks in organic chemistry, with applications ranging from biochemistry to material sciences. Traditional alkynylation reactions rely on the use of acetylenes as nucleophiles. However, the discovery and development of ethynyl hypervalent iodine reagents have greatly expanded the transfer of alkynes as electrophilic synthons. This feature article presents the progress in the field since 2018, including synthesis of alkynyl hypervalent iodine reagents, their use in base-mediated and transition-metal catalyzed alkynylations, and progress in radical-based alkynylations and atom-economical transformations.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Stephanie G. E. Amos, Franck Le Vaillant, Jerome Waser
Summary: Alkynes and nitriles are important building blocks in organic synthesis, chemical biology, and materials science. This study investigates the conversion of alcohols into alkynes and nitriles using cesium oxalates and Ethynyl BenziodoXolones (EBXs), and explores the effects of backbone modification of EBXs on the deoxyalkynylation of cesium oxalates. Preliminary data on the development of new deoxycyanation and dethioalkynylation processes are also presented, along with the serendipitous discovery of C-H alkynylation of 1,2-dichloroethane.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Emma G. L. Robert, Vincent Pirenne, Matthew D. Wodrich, Jerome Waser
Summary: A convenient method for the one-step synthesis of beta-aminocyclobutane monoesters using commercially available reagents is reported. The obtained strained rings undergo dearomative annulation with indole partners using silylium catalysis, providing tricyclic indolines with four new stereocenters. The reaction can proceed both intra- and intermolecularly and the outcome can be selectively controlled based on reaction temperature, resulting in the formation of either akuamma or malagasy alkaloid-like tetracyclic structures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xing-Yu Liu, Xinjian Ji, Christian Heinis, Jerome Waser
Summary: We present a new method for modifying peptides using highly reactive hypervalent iodine reagents called ethynylbenziodoxolones (EBXs). These peptide-EBXs can be easily synthesized through solution- and solid-phase peptide synthesis (SPPS). They can be used to couple peptides to other peptides or proteins via reaction with Cys, resulting in thioalkynes in organic solvents or hypervalent iodine adducts in water buffer. Additionally, a photocatalytic decarboxylative coupling to the C-terminus of peptides was developed, leading to macrocyclic peptides with unprecedented crosslinking.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nieves P. P. Ramirez, Jerome Waser
Summary: An asymmetric 3-component reaction catalyzed by a Cu-I-BOX catalyst was developed for the synthesis of chiral trifluoromethylated propargyl ethers and anilines. The reaction showed high enantioselectivity and yield with various nucleophiles and different electrophiles. The method also exhibited good diastereoselectivity with chiral substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Eliott Le Du, Nieves P. Ramirez, Stefano Nicolai, Rosario Scopelliti, Farzaneh Fadaei-Tirani, Matthew D. Wodrich, Durga Prasad Hari, Jerome Waser
Summary: First synthesized in 1991, EthynylBenziodoXolones (EBXs) are now among the most versatile electrophilic alkynylation reagents. Due to their cyclic structure, these reagents exhibit enhanced stability compared to previously used alkynyl iodonium salts. The collected structural data of EBXs and their analogues, along with the calculated molecular electrostatic potentials (MEP), is expected to be highly useful for further developments in the field, considering the tight relationship between structure and reactivity in hypervalent iodine reagents.
HELVETICA CHIMICA ACTA
(2023)
Article
Chemistry, Multidisciplinary
Ruru Chen, Jian Zhao, Yifan Li, Yi Cui, Ying-Rui Lu, Sung-Fu Hung, Shifu Wang, Weijue Wang, Guodong Huo, Yang Zhao, Wei Liu, Junhu Wang, Hai Xiao, Xuning Li, Yanqiang Huang, Bin Liu
Summary: By using experimental and theoretical methods, the metastable state of single-atom Sn in copper oxide was tracked and identified, providing a theoretical basis for the highly selective CO2 electroreduction to CO.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Shunqin Luo, Hui Song, Fumihiko Ichihara, Mitsutake Oshikiri, Wenning Lu, Dai-Ming Tang, Sijie Li, Yunxiang Li, Yifan Li, Philo Davin, Tetsuya Kako, Huiwen Lin, Jinhua Ye
Summary: In this study, a light activation strategy was demonstrated to regulate the dynamic restructuring of Cu active sites in a TiO2-supported Cu catalyst during low-temperature methanol steam reforming. The thermally deactivated Cu/TiO2 underwent structural restoration from Cu2O to metallic Cu under illumination, leading to significantly enhanced activity and stability. The optimized Cu/TiO2 exhibited a high H-2 production rate under low-intensity solar irradiation, outperforming conventional photocatalytic and thermocatalytic processes. The results suggest the feasibility of real-time functionalization of catalysts through the strong light-matter-reactant interaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Vladyslav Smyrnov, Jerome Waser
Summary: An electrophile-induced semipinacol rearrangement of cyclopropenylcarbinols is described, enabling the synthesis of polyfunctionalized cyclopropanes under mild metal-free conditions. The reaction demonstrates broad scope, accommodating various electrophiles, migrating groups, and substitution patterns on the cyclopropene. It is particularly useful for the synthesis of small ring-containing spirocycles, which are important building blocks in medicinal chemistry.
Article
Chemistry, Organic
Pierre Palamini, Julien Borrel, Mael Djaid, Morgane Delattre, Jerome Waser
Summary: We report the synthesis of ketene dithioarylacetals in 40-97% yield using thiophenols and acyl-EBXs generated in situ from a common hypervalent iodine precursor and alkynyl trifluoroborate salts. The products could be further modified to afford functionalized ketene dithioacetals and various S-substituted heterocycles.
Article
Chemistry, Multidisciplinary
Julien Borrel, Jerome Waser
Summary: We present a method for azidoalkynylation of alkenes, which provides a straightforward route to homopropargylic azides by using hypervalent iodine reagents and alkynyltrifluoroborate salts. The development of a photocatalytic redox-neutral radical polar crossover process was crucial for this transformation. A range of homopropargylic azides with electron-rich and -poor aryls, heterocycles, or ether substituents could be obtained in yields of 34-84%. These products serve as valuable building blocks that can be easily converted into pyrroles or bioactive amines.
Article
Chemistry, Multidisciplinary
Ruru Chen, Jian Zhao, Yifan Li, Yi Cui, Ying-Rui Lu, Sung-Fu Hung, Shifu Wang, Weijue Wang, Guodong Huo, Yang Zhao, Wei Liu, Junhu Wang, Hai Xiao, Xuning Li, Yanqiang Huang, Bin Liu
Summary: By using experimental and theoretical approaches, this study successfully tracked and identified the metastable state of single-atom Sn in copper oxide, providing fundamental insights for the highly selective electroreduction of CO2 to produce CO.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Computer Science, Artificial Intelligence
Likun Xia, Yuan Feng, Ziheng Guo, Jinhong Ding, Yanlei Li, Yifan Li, Ming Ma, Guoxi Gan, Yehan Xu, Jingyu Luo, Zhiping Shi, Yong Guan
Summary: This study proposes an early detection framework based on EEG data for reducing the risk of mental stress-related diseases. The framework, called MuLHiTA, utilizes a multibranch LSTM and hierarchical temporal attention approach to effectively identify mental stress levels. Experimental results demonstrate that MuLHiTA outperforms state-of-the-art algorithms, showcasing its viability for early detection of mental stress.
IEEE TRANSACTIONS ON NEURAL NETWORKS AND LEARNING SYSTEMS
(2023)
