Article
Chemistry, Multidisciplinary
Yuse Kuriyama, Yusuke Sasano, Yoshihiko Hoshino, Shun-ichiro Uesugi, Aoto Yamaichi, Yoshiharu Iwabuchi
Summary: Highly regioselective intramolecular aminolysis of 3,4-epoxy amines has been achieved by chemoselective activation of epoxides in the presence of unprotected aliphatic amines in the same molecules using a La(OTf)(3) catalyst, resulting in excellent regioselectivity for anti-Baldwin 5-endo-tet cyclization and stereospecific formation of 3-hydroxy-2-alkylpyrrolidines in high yields. DFT calculations suggested that regioselectivity is attributed to distortion energies of epoxy amine substrates. This reaction was used in the enantioselective synthesis of an antispasmodic agent prifinium bromide.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Gregorio Guzman-Gonzalez, Soline Vauthier, Marta Alvarez-Tirado, Stephane Cotte, Laurent Castro, Aurelie Gueguen, Nerea Casado, David Mecerreyes
Summary: A family of single-ion lithium conducting polymer electrolytes based on highly delocalized borate groups has been reported, with the effect of substituents on boron atom analyzed. The polymer with flexible and electron-withdrawing substituents demonstrates the highest ionic conductivity among reported lithium single-ion conducting homopolymers. Combining high lithium transference number and good electrochemical stability, it shows promise for application in lithium batteries.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Kazuki Inaba, Yuna Naito, Mina Tachibana, Kazunobu Toshima, Daisuke Takahashi
Summary: A regioselective and beta-stereospecific d-/l-arabinofuranosylation method has been developed for efficient synthesis of biologically active natural glycosides. The method showed high regioselectivity and yield with complete beta-stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yi Peng, Martin Oestreich
Summary: Opening the ring of cyclic amines by selectively breaking the carbon-nitrogen bond greatly expands the range of available nitrogen-containing structures. However, methods that can directly open secondary amines are limited. This study presents an efficient reductive ring opening of cyclic amines using PhSiH3 under B(C6F5)(3) catalysis, allowing for the transformation of unstrained cyclic amines into acyclic amines in a simple one-step process. Experimental evidence supports a stepwise mechanism involving silylammonium ions and reductive cleavage of carbon-nitrogen bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Hao Liu, Xin He, Zhicheng Chen, Jingchao Zhang, Xinjie Fang, Zhizhong Sun, Wenyi Chu
Summary: N-trifluoromethylsuccinimide (NTFS), a new trifluoromethylation reagent, was synthesized via Ag-CF3 and successfully applied for the direct trifluoromethylation of free aniline, yielding a series of trifluoromethyl products with high efficiency. The practicality of this method was demonstrated through a gram-scale experiment and the synthesis of the antiasthmatic drug Mabuterol. Furthermore, a possible radical mechanism was proposed and confirmed by relevant experiments. This protocol offers a new solution for the C-H trifluoromethylation of free anilines.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Peng-Fei Yang, Jian-Xing Liang, Han -Tong Zhao, Wei Shu
Summary: In this study, a straightforward method to access enantioenriched 1,n-diamines containing a chiral alpha-branched aliphatic amine is achieved through Ni-catalyzed asymmetric hydroamination. This method delivers good yields and excellent enantioselectivities with diverse substitution patterns, and exhibits excellent functional group tolerance.
Article
Chemistry, Organic
Venkati Bethi, Syeda Bakhtawar Zahra, Bapuaro D. Rupanawar, Fujie Tanaka
Summary: This article describes the regioselective aldol reactions of beta-methyl-substituted cyclic enone derivatives with isatins using a catalyst system composed of DBU, pyrrolidine, and DMSO. The reactions resulted in aldol products with bond formation at the methyl group of the beta-methyl-substituted cyclic enone derivatives. This method selectively affords gamma-position-reacted aldol products, expanding the scope of concisely synthesized 3-substituted 3-hydroxyoxindole derivatives.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Zhicheng Bao, Meirong Huang, Yan Xu, Xinhao Zhang, Yun-Dong Wu, Jianbo Wang
Summary: Bisborylalkanes are versatile bifunctional reagents in organic synthesis, with the ability to selectively convert their two boron moieties into other functional groups. This study presents a new strategy for synthesizing bisborylalkanes through the reaction of N-trisylhydrazones with diboronates, resulting in the transformation of bis(boryl) methane into 1,2-bis(boronates) through formal carbene insertion. This practical synthesis method allows for the broad substrate scope of 1,2-diboronates by readily deriving N-trisylhydrazones from corresponding aldehydes. Mechanistic studies uncover an unusual neighboring group effect of 1,1-bis(boronates) that explains the observed regioselectivity when unsymmetric 1,1-diboronates are utilized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Hubert Hettegger, Andreas Hofinger, Thomas Rosenau
Summary: The regioselectivity of the reaction between 2,5-dihydroxy-[1,4]-benzoquinone (DHBQ) and diamines has been explained using an adapted theory of strain-induced bond localization (SIBL). Simple computations can accurately predict the product structure based on bond spacings and geometries.
CURRENT ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Ben Liu, Yoshinao Nakagawa, Mizuho Yabushita, Keiichi Tomishige
Summary: This study investigated the hydrogenolysis of 1, 2-diols to primary and secondary alcohols using Ir-FeOx catalysts supported on nonoxides. It was found that BN effectively supported the hydrogenolysis of 1, 2-butanediol to produce 2-butanol, similar to previous findings with rutile TiO2. The addition of Fe species to Ir/BN greatly enhanced catalytic activity, while other supports, such as carbon, mainly produced primary alcohols.
Review
Chemistry, Physical
Longli Ma, Jian Tan, Yuan Wang, Zhu Liu, Yifan Yang, Tia Gray, Xiang Zhang, Mingxin Ye, Jianfeng Shen
Summary: With the development of energy storage technology, the demand for high energy density and high security batteries is increasing, making the research of lithium battery (LB) technology an extremely important pursuit. However, the poor structural stability of electrode materials, high interfacial impedance between electrolyte and electrode, and the growth of lithium dendrites have seriously hindered the commercialization of LBs. Recently, boron-based materials have been widely used in different LB components to resolve these problems.
ADVANCED ENERGY MATERIALS
(2023)
Article
Materials Science, Ceramics
Jiatai Wang, Yuanyuan Li, Shishi Wei, Shunli Hou, Geng Zhou, Xiaocen Yan, Ruheng Xi, Xiaoyi Hou
Summary: Through doping B3+ using a high-temperature solid-phase method, the electrochemical properties of the LiNi0.815Co0.15Al0.035O2 cathode (NCA) were significantly improved. X-ray diffraction analysis and Rietveld refinement showed that B3+ enhanced lattice ordering by minimizing Li+/Ni2+ mixing. Scanning electron microscopy observations indicated that B3+ doping changed the particle morphology. The specific discharge capacities of 1.5% B-NCA were 178.31 and 123.74 mAhg 1 at 0.2 and 5C, respectively. After 100 cycles, the specific discharge capacity was 176.29 mAhg 1 at 0.2C with a capacity retention of 98.87%. Boron doping significantly improves the structural stability of nickel-rich cathode materials by suppressing the detrimental H2 & RARR;H3 phase transition, thus improving the electrochemical performance of nickel-rich ternary lithium-ion batteries.
CERAMICS INTERNATIONAL
(2023)
Article
Chemistry, Physical
Takumi Tsushima, Hideya Tanaka, Kazuki Nakanishi, Masaaki Nakamoto, Hiroto Yoshida
Summary: The highly internal-selective borylation of terminal alkynes under copper catalysis was achieved by diminishing boron-Lewis acidity and introducing ligand-derived steric bulk around a copper center. The use of an anthranilamide-substituted boron moiety enabled internal regioselectivity and Suzuki-Miyaura cross-coupling activity to be compatibly achieved, providing a direct and universal approach to variously substituted branched alkenylboron compounds.
Review
Chemistry, Organic
Rajan Archana, Thaipparambil Aneeja, Gopinathan Anilkumar
Summary: This review provides an overview of the research progress in ruthenium-catalyzed allylic amination reactions, including a summary and analysis of the literature up to 2021.
CURRENT ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Tuoya Naren, Ruheng Jiang, Piao Qing, Shaozhen Huang, Canhui Ling, Jialin Lin, Weifeng Wei, Xiaobo Ji, Yuejiao Chen, Qichun Zhang, Gui-Chao Kuang, Libao Chen
Summary: This study designs a lithium metal battery combining agraphene oxide-poly(ethylene oxide) functionalized polypropylene separator and lithium-boron anode to solve the problems of dendrite growth, interfacial reactions, and volume change. The results show that the battery exhibits good ionic conductivity, electrolyte uptake, and high electrochemical stability. The synergistic effect of the functionalized separator and lithium-boron anode provides a direction for the development of high-performance lithium metal batteries.
Article
Chemistry, Multidisciplinary
Biao Cheng, Yu Chen, Peng Zhou, Zuowei Xie
Summary: A new method for the trifunctionalization of o-carboranes has been developed, leading to the synthesis of a new class of B(3,4,5)-trisubstituted o-carborane derivatives. This method involves a series of reactions and represents a new strategy for the catalytic selective polyfunctionalization of carboranes with different substituents, achieving high yields of the desired products.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Peng Zhou, Yu Chen, Zuowei Xie
Summary: In this study, a highly efficient iron-catalyzed method for the 4/5-fold cage B-H methylation/arylation of carboranes was developed without the need for noble transition metal catalysts. The reaction used organo-aluminum compounds as alkylation/arylation reagents and diethyl oxalate as an inexpensive oxidant, resulting in the synthesis of various compounds with good yields. This method represents an alternative strategy for the catalytic selective polyfunctionalization of carboranes via base metal catalysis.
Article
Chemistry, Organic
Lin-Bao Zhang, Zuowei Xie
Summary: We report a catalytic selective cage B4-H amination of o-carboranes using an Ir(III) complex as a catalyst and anthranils as aminating agents. This reaction allows for the synthesis of a large class of B4-aminated o-carboranes with high yields and broad substrate scope under mild conditions without any oxidants.
Article
Chemistry, Organic
Shimeng Li, Jie Zhang, Zuowei Xie
Summary: This work describes a general method for the efficient production of a class of cage B-centered carboranyl radicals, which are useful intermediates for the preparation of a family of cage B-(hetero)arylated o-carboranes.
Article
Chemistry, Multidisciplinary
Huifang Zhang, Ruofei Cheng, Zaozao Qiu, Zuowei Xie
Summary: An efficient Ir-catalyzed cage boron alkenylation of 1-(2 '-picolyl)-o-carboranes with diarylacetylenes has been developed, leading to a wide variety of B-H geminal addition products via 1,2-carbon migration of alkynes. The steric effect of cage carbon substituents has a great impact on the regioselectivity of such alkenylation reactions.
CHEMICAL COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Organic
Varinder K. K. Aggarwal, Zuowei Xie, Hajime Ito
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Liping Guo, Shaowu Wang, Zuowei Xie
Summary: Rare-earth metal carboryne complexes were synthesized using either an alkane elimination reaction or a salt metathesis reaction. Single-crystal X-ray analyses confirmed the molecular structures, showing a unique three-membered ring between the rare-earth metal and two cage C atoms. These complexes underwent ring-expansion reactions with various unsaturated organic compounds to form five-membered metallacycles.
Article
Chemistry, Multidisciplinary
Yik Ki Au, Qiangqiang Ma, Jie Zhang, Zuowei Xie
Summary: An efficient and convenient strategy for Ir-catalyzed selective B(3)-amination of o-carboranes with amines via acceptorless BH/NH dehydrocoupling was developed, resulting in a series of B(3)-aminated-o-carboranes with moderate to high yields and H2 gas as the sole by-product. The oxidant-free system demonstrates sustainability, atom-economy, and environmental friendliness. A reaction mechanism involving an Ir(I)-Ir(III)-Ir(I) catalytic cycle with oxidative addition, dehydrogenation, and reductive elimination was proposed.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Zhen Nie, Ruofei Cheng, Zaozao Qiu, Zuowei Xie
Summary: 4-Bpin-o-carborane exhibits a unique reactivity with ketones under basic conditions, leading to sequential cage carbon alkylation, B-B bond activation, and unexpected O-migration. The reaction is compatible with a wide range of substrates including dialkyl or alkyl aryl ketones. The proposed reaction mechanism involves cage CH deprotonation, nucleophilic attack of ketone, and O-migration along with B-B bond cleavage.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Shimeng Li, Yizhen Liu, Zuowei Xie
Summary: This work presents a general method for synthesizing sulfenylated and selenylated carboranes at room temperature using iodocarboranes as starting materials. The generation of hypervalent boron radicals via a visible light-promoted Pd(0)/Pd(I) pathway allows for the convenient construction of B-S/Se bonds.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Huifang Zhang, Jie Zhang, Zaozao Qiu, Zuowei Xie
Summary: The intrinsic chirality of three-dimensional carborane derivatives was established by studying the substitution patterns. Through the addition of functional groups, the symmetrical o-carborane can be transformed into chiral-at-cage structures. An Ir-catalyst-promoted asymmetrical (S)-B(4)-H activation method under mild reaction conditions was developed, achieving high efficiency with up to 99% enantioselectivity.
Article
Chemistry, Organic
Jie Zhang, Zuowei Xie
Summary: This paper summarizes the recent developments in base metal-catalyzed regioselective B-H functionalization of carboranes, particularly in the regio- and enantio-selective cage B-H derivatization among ten chemically similar BH vertices in o-carboranes. While precious transition metal-catalyzed cage B-H functionalization has made significant advances in diversely functionalized o-carboranes, research on B-H functionalization via a base metal catalysis strategy has just begun recently.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Peng Zhou, Yu Chen, Zuowei Xie
Summary: This paper reports a highly efficient iron-catalyzed, silver-free B-H methylation/arylation reaction of carboranes using organoaluminum compounds as reagents, leading to the synthesis of various substituted carboranes with excellent yields. This method allows for easy gram-scale synthesis and the proposed reaction mechanism provides insight into the process.
Article
Chemistry, Multidisciplinary
Hairong Lyu, Zuowei Xie
Summary: A unique approach to vertex-selective catalytic B-H amination has been developed, allowing the reaction to occur at either the B(3)- or B(4)-position in o-carboranes. By using different transition metal catalysts, the dehydrogenative BH/NH cross-coupling of o-carboranes and free amines has been achieved, resulting in a wide variety of B(3)- or B(4)-aminated o-carboranes with high regioselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Zaozao Qiu, Zuowei Xie
Summary: Carborynes, three-dimensional analogues of benzyne, can be generated in situ from specific precursors. They are useful for synthesizing various functionalized carborane derivatives and exhibit unique properties. Carborynes exhibit pericyclic reaction modes similar to benzyne, but also have their own distinctive features. Previous research has explored the unique reaction modes and mechanisms of carborynes.
CHEMICAL SOCIETY REVIEWS
(2022)
