Article
Multidisciplinary Sciences
Shuai Liu, Xu Cheng
Summary: The authors demonstrate a novel methodology for the synthesis of aromatic heterocycles containing nitrogen by electrochemically inserting nitrogen atoms into a carbon ring using ammonia. This approach offers high atom and step economy, making it valuable for extensive applications in chemical and biological research, with significant potential for drug development.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Hang Li, Na Li, Jinghao Wu, Tianyang Yu, Ran Zhang, Li-Ping Xu, Hao Wei
Summary: In this study, a method for direct insertion of an intramolecular nitrogen atom into an aromatic C-C bond was described. Carbamoyl azides were activated by a Rh catalyst and inserted directly into the C-C bond of an arene ring to produce fused azepine products. The use of a paddlewheel dirhodium complex effectively inhibited the undesired C-H insertion. Density functional theory calculations were used to elucidate the reaction mechanism and chemoselectivity of the Rh-catalyzed reactions. The resulting fused azepine products are highly stable and can be further diversified.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jian Luo, Ai-Qing Zhong, Jia-Hao Qiu, Xiong-Wei Liu, You-Ping Tian, Bao-Hua Zhang, Guo-Shu Chen, Wei Shu, Yun-Lin Liu
Summary: A green and environmentally friendly synthetic approach has been developed for the preparation of racemic or enantioenriched 3,4,6-trisubstituted α-pyrones through a cheap K2CO3-catalyzed C(CO)-C bond insertion reaction of ketenimines with 1,3-diketones. The synthetic utility of this methodology was demonstrated by the broad substrate scope and the concise synthesis of analogues of pharmaceutically active compounds. Furthermore, the study also revealed the potential of extended conjugated α-pyrones for optoelectronic applications in organic light-emitting diodes.
Article
Chemistry, Inorganic & Nuclear
Julien Petit, Anthony Cavaille, Nathalie Saffon-Merceron, Marie Fustier-Boutignon, Nicolas Mezailles
Summary: The reduction of a high spin paramagnetic complex by two electrons under N-2 resulted in the formation of two isomeric low spin diamagnetic complexes, which were successfully isolated and characterized. DFT calculations provided insights into the mechanism of double alpha,alpha CH bond insertion into a single sp(3) CH2 moiety. Fast exchange positions of hydrides in the cis dihydride complex were observed using NMR spectrocscopy.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Xiao-Yuan Cui, Zhong-Tian Ye, Hai-Hong Wu, Chang-Ge Ji, Feng Zhou, Jian Zhou
Summary: We report on a metal-catalyzed formal intermolecular carbene insertion reaction into the vinylic C(sp(2))-H bond of alkenes, with Au(I) catalyst proving to be the most efficient among the screened metal catalysts. This reaction provides a facile method to access C4-alkenyl isochromanones and isoquinolinones from corresponding diazo reagents and alpha-methylstyrenes, with moderate to good yields, and excellent chemoselectivity. Mechanistic studies suggest the existence of two possible reaction pathways: nucleophilic attack-selective elimination by the gold-carbenoid and cyclopropanation-ring-opening-olefin isomerization process. The structure of the diazo reagents has a significant impact, as diazo(thio)oxindoles react with alpha-methylstyrenes via formal allylic C(sp(3))-H insertion to afford 3-allyl(thio)oxindoles.
Article
Chemistry, Organic
Yongquan Ning, Qingmin Song, Paramasivam Sivaguru, Lizuo Wu, Edward A. Anderson, Xihe Bi
Summary: In this study, we reported a silver-catalyzed reaction that enables the insertion of alkynyl carbenes into beta-ketocarbonyls, providing trisubstituted allenyl ketones. This reaction represents the first example of alkynyl carbene insertion into C-C sigma bonds, resulting in products with an sp(2) carbon center. The obtained products serve as useful substrates for further transformations.
Article
Chemistry, Organic
Zichen Wang, Huaquan Fang, Guixia Liu, Zheng Huang
Summary: In this study, a pincer Ru-catalyzed dual intramolecular dehydrogenative silylation of primary C(sp(3))-H bonds was reported. The reaction demonstrated high efficiency, scalability, and good functional group tolerance, allowing for facile and atom-economical access to structurally diverse silicon-centered spirocycles, including unprecedented oxa-spirosilabiindanes and aza-spirosilabiindanes.
Article
Chemistry, Organic
Ethan H. Spielvogel, Bernard G. Stevenson, Michael J. Stringer, Yue Hu, Lisa A. Fredin, John R. Swierk
Summary: Despite the widespread use of photoredox coupled hydrogen atom transfer (HAT) reactions, the precise mechanism and kinetics are poorly understood. This report presents a mechanistic study of a prototypical tandem photoredox/HAT reaction coupling cyclohexene and 1,4-dicyanobenzene using an Ir(ppy)(3) photocatalyst and thiol HAT catalyst. Key unproductive pathways and side products were identified, with the reaction efficiency being limited by parasitic absorption and unproductive quenching.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Zijie Lin, Zhenjie Zheng, Rongxing Xiao, Kangcheng Zheng, Juping Wang
Summary: This study investigates the mechanism and reactivity of Ir-catalyzed alpha-amidation of 2-acylimidazoles, with a focus on nitrene insertion selectivity. The results show that the catalytic mechanism involves iridacycle formation, CO2 release, nitrene insertion, and amido protonation processes. Nitrene insertion is identified as the rate-determining and selectivity-determining step. The study also reveals the preference of the nitrene group to insert into an Ir-C alpha bond over a C gamma-H bond, and the difference in reactivity between alpha-mono- and alpha,alpha-di-substituted 2-acylimidazoles.
Article
Chemistry, Multidisciplinary
Dong -Kai Wang, Liu-Bin Li, Fa-Liang Liu, Hui Qiu, Jiao-Zhe Li, Jianfeng Zhang, Chao Deng, Wen-Ting Wei
Summary: This study presents a novel method for the construction of all-carbon quaternary centers, specifically those with an alkyne-substituted framework, using a Fe-catalyzed formal insertion of diazo compounds into C(sp)-C(sp(3)) bonds of propargyl alcohols under mild conditions.
ACS CENTRAL SCIENCE
(2022)
Article
Chemistry, Organic
Fang Wang, Jiaming Chen, Xiaoqi Jia, Dailin Zhuang, Zhenyang Wan, Lifang Ma, Ziyuan Li
Summary: A remote directing group-enabled radical relay strategy for benzylic direct C(sp3)-H alkoxylation with alcohols at room temperature is developed, which achieves satisfactory site-selectivity, chemoselectivity, and reaction scope under simple and mild conditions without the need for ligands or additives.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Neha Jha, Roushan Prakash Singh, Paridhi Saxena, Manmohan Kapur
Summary: An Ir(III)-catalyzed C(3)-H alkylation of N-acetyl-1,2-dihydroisoquinolines with diverse acceptor-acceptor diazo compounds has been achieved under a single catalytic system via metal carbene migratory insertion. Further synthetic transformations of the alkylated products lead to the formation of several synthetically viable isoquinoline derivatives with immense potentials.
Article
Chemistry, Organic
David F. Fernandez, Maria Gonzalez-Esguevillas, Sebastian Keess, Felix Schafer, Jens Mohr, Andre Shavnya, Thomas Knauber, David C. Blakemore, David W. C. MacMillan
Summary: We present a general approach to synthesis of diversified libraries featuring aliphatic core rings via photoredox catalysis under mild conditions.
Article
Chemistry, Organic
Javeed Ahmad Tali, Ravi Shankar
Summary: Here, we report an unprecedented protocol using ruthenium-catalyzed annulation for the synthesis of 6H-chromeno[4 ',3 ':4,5]imidazo[1,2-a]pyridin-6-one, and a new method for intramolecular chelation-assisted C-H activation to produce functionalized 2-(3-formylimidazo[1,2-a]pyridin-2-yl)phenyl acetate. Furthermore, a one-pot approach using ruthenium catalysis and formic acid has been developed for the gram-scale synthesis of bis(2-phenylimidazo[1,2-a]pyridin-3yl)methane (BIP) and the late-stage functionalization of zolimidine, a marketed drug, with good yield.
Article
Chemistry, Applied
Hisanori Nambu, Ryoya Amano, Takafumi Tamura, Takayuki Yakura
Summary: This study describes the dirhodium(II)-catalyzed intramolecular insertion of aryldiazoacetates into unactivated primary C-H bonds. The reaction shows high selectivity and provides a direct route to 2-unsubstituted indane-1-carboxylates and specific isomers with ortho-substituted groups. Furthermore, a chemoselective C-H insertion reaction of aryldiazoacetate with a 1-oxyethyl substituent is achieved using a specific protecting group.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Xiaofeng Mao, Jie Zhang, Zhenpin Lu, Zuowei Xie
Summary: A tetra(o-tolyl)(mu-hydrido)diborane(4) anion 1 was synthesized and found to form eta(2)-B-B bonded complexes 2 with NHC-coordinated transition-metal halides, where the elongation of B-B bonds is most significant in the gold complex.
Article
Materials Science, Multidisciplinary
Ming Chu, Jie Zhang, Xingwei Zeng, Zefeng Chen, Danqing Liu, Han Chen, Zuowei Xie, Jianbin Xu, Qian Miao
Summary: Molecules of 12-o-carboranyldodecylphosphonic acid can form a novel self-assembled monolayer on alumina, effectively tuning charge carriers in organic field effect transistors by assembling dipoles at the semiconductor-dielectric interface. This SAM enables p-channel OFETs of pentacene and ambipolar charge transport in n-type organic semiconductors like chlorinated tetraazapentacene, while the surface electrostatic potential of the SAM correlates with the observed shift of threshold voltage in OFETs.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Jie Zhang, Zuowei Xie
Summary: This study reported a pyridine-enabled transition-metal-free regioselective nucleophilic aromatic cage B(4)-H amination reaction, offering a selective amination strategy for o- and m-carboranes. Control experiments indicated the crucial role of magnesium complex, bidentate ligand, and reaction temperature in the process of cage isomerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Shimeng Li, Zuowei Xie
Summary: A strategy for the generation of hypervalent boron-centered carboranyl radicals at the B(3), B(4), and B(9) positions has been developed for the first time via visible-light-promoted iodine atom abstraction. These radicals react with various substrates to afford a wide range of carborane derivatives.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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)
