Article
Chemistry, Organic
Jianwen Jin, Andres Felipe Leon Rojas, Yichao Zhao, Sara Helen Kyne, Bo Xia, Bingwei Zhong, Philip Wai Hong Chan
Summary: This study presents a synthetic method for efficiently preparing (E)-3-arylazoindoles, which does not require the exclusion of air or moisture and can be conducted under mild reaction conditions. The suggested mechanistic pathway of the azo coupling reaction reveals the unique electrophilic behavior of α-diazocarbonyl compounds. Experimental studies provide insights into the preferential generation of a (1H-indol-3-yl)gold species and its impact on the regio- and chemoselectivity of the products. The utility of this synthetic method has been demonstrated in the synthesis of specific molecules, molecular switch assembly, and late-stage functionalization of biologically relevant molecules.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Marcel Haerterich, Benedikt Ritschel, Merle Arrowsmith, Julian Boehnke, Ivo Krummenacher, Ashwini K. Phukan, Holger Braunschweig
Summary: This study reports the first examples of thermally induced, transition-metal-free cross-metathesis between an organic alkyne and inorganic B=B double bonds, resulting in the formation of novel compounds with unique properties. These compounds form via a biradical mechanism and possess distinctive reducibility.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Xiai Luo, Yu Zhao, Susu Tao, Zhong-Tao Yang, Hui Luo, Weiguang Yang
Summary: A simple synthesis method for (Z)-1,2-dihydro-2-iminoquinolines has been achieved using copper-catalyzed reaction of 1-(2-aminophenyl)ethan-1-ones, sulfonyl azides, and terminal ynones under mild conditions. The Z-configured products are obtained through a base-free CuAAC/ring-opening process due to hydrogen bonding.
Article
Chemistry, Physical
An T. Ho, Seth C. Ensign, Evan P. Vanable, David Portillo, Jenna N. Humke, Gregory D. Kortman, Kami L. Hull
Summary: The Ir-catalyzed regioselective hydroamination of allyl amines and the catalyst-controlled regiodivergent hydroamination of homoallylic amines with aniline nucleophiles have been reported. These reactions can selectively synthesize diamines at different positions, and exhibit good reaction yields.
Article
Chemistry, Organic
Chen-Long Li, Yusheng Yang, Yi Zhou, Zhi-Xiang Yu
Summary: A formal [3+3+1] reaction was developed through gold(I)-catalyzed enyne cycloisomerization and rhodium(I)-catalyzed [6+1] reaction to synthesize aza-6/7 bicyclic compounds, hexahydrocyclohepta[c]pyridinones. DFT calculations revealed four steps involved in the [6+1] cycloaddition reaction of vinylspiropentanes and CO.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Gargi Chakraborti, Tirtha Mandal, Charles Patriot Roy, Jyotirmayee Dash
Summary: A cascade sequence involving [3+2] cycloaddition, 1,2-acyl migration and hydrolysis produces 2H-1,2,3-triazoles with regioselectivity, using a CuI-prolinamide catalyst system in aqueous media. Prolinamide promotes novel organocatalytic 1,2-acyl migration and hydrolysis of N-2-carboxyalkylated triazoles in the reaction.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Organic
Wei-Cheng Zhao, Xin Wang, Juhua Feng, Ping Tian, Zhi-Tao He
Summary: A novel and straightforward palladium-catalyzed desymmetric [2+2+2] cycloaddition reaction has been established, leading to the diastereoselective preparation of widely existing fused tricyclic organic compounds in moderate to excellent yields. A one-step aromatization process provides facile access to benzene-containing tricycles from the above cycloaddition products.
Article
Chemistry, Organic
Zhiqiang Zhang, Luxin Chen, Ying Wang, Weikai Dai, Pengfei Li, Zhen Yang, Xiuhuan Li, Huaiji Zheng
Summary: An effective method for synthesizing furans is developed using a tandem 1,2-acyloxy migration/intramolecular [3 + 2] cycloaddition/aromatization reaction of enol ether-tethered propargylic esters. This reaction demonstrates excellent functional group tolerance, broad substrate scope, and excellent chemoselectivity. The isolation of dihydrofuran intermediates in some cases provides further insight into the [3 + 2] cycloisomerization process.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yoshihiro Oonishi, Shunki Sakamoto, Shuya Agata, Yoshihiro Sato
Summary: In the Rhodium(I)-catalyzed enantioselective cyclization of enynes, the presence of different functional groups on the substrate molecules affects the structure and yield of the products, with C(sp(3))-H bond activation being an important high energy barrier step in the cyclization reaction.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Physical
Ryota Abe, Yuki Nagashima, Jin Tanaka, Ken Tanaka
Summary: The development of an operationally simple method for diversity-oriented fluoranthene synthesis is important in the field of organic synthesis due to the presence of the fluoranthene skeleton in natural products and fluorescent materials. In this study, substituted fluoranthenes and azafluoranthenes were synthesized at room temperature through a cationic Rh(I)/H8-BINAP complex-catalyzed [2 + 2 + 2] cycloaddition reaction using 1,8-dialkynylnaphthalenes. Both theoretical and experimental studies revealed that noncovalent interactions between the phenyl groups on the substrates and ligand stabilize the transition states, facilitating the sterically demanding reactions.
Article
Chemistry, Physical
Jiwoo Jeong, Hoimin Jung, Dongwook Kim, Sukbok Chang
Summary: Herein, we report a tailored catalyst system for outer-sphere C-H amidations. Through high-throughput experimentation, we identified the optimal catalyst and achieved efficient reactions.
Article
Chemistry, Multidisciplinary
Wenxin Lu, Yongmei Zhao, Fanke Meng
Summary: This study presents the catalytic sequential hydrosilylation of 1,3-enynes and 1,4-enynes promoted by cobalt complexes derived from bisphosphines. The reactions resulted in the formation of enantioenriched cyclic alkenylsilanes with simultaneous construction of a carbon-stereogenic center and a silicon-stereogenic center. The functionalization of these chiral silanes provides access to a variety of difficult-to-access chiral building blocks.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Ryota Abe, Yuki Nagashima, Jin Tanaka, Ken Tanaka
Summary: Developing a simple method for synthesizing diverse fluoranthene skeletons is crucial in organic synthesis. Existing methods have limitations in reaction conditions and substrate applicability. This study presents a room temperature synthesis of substituted fluoranthenes and azafluoranthenes using cationic Rh(I)/H-8-BINAP complex-catalyzed cycloaddition. The reactions were stabilized by the H-8-BINAP ligand, and noncovalent interactions between phenyl groups on the substrates and ligand accelerated the reaction.
Article
Chemistry, Physical
Ryota Abe, Yuki Nagashima, Jin Tanaka, Ken Tanaka
Summary: The development of a simple method for diversity-oriented fluoranthene synthesis is important in organic synthesis due to the widespread occurrence of fluoranthene in natural products and fluorescent materials. In this study, we report the room temperature synthesis of substituted fluoranthenes and azafluoranthenes using a cationic Rh(I)/H-8-BINAP complex-catalyzed [2 + 2 + 2] cycloaddition. The reaction is enabled by the stabilization of intermediates by the H-8-BINAP ligand. The noncovalent interactions between the phenyl groups on both the substrates and the ligand play a crucial role in accelerating the sterically demanding reactions.
Article
Chemistry, Multidisciplinary
Zitong Zhou, Danyang Luo, Guanrong Li, Zhongtao Yang, Liao Cui, Weiguang Yang
Summary: An efficient and simple three-component cascade reaction was reported, providing a variety of polysubstituted imidazo[1,2-a]pyridine derivatives in moderate to excellent yields. The reaction proceeds through a CuAAC/ring-cleavage process and forms a highly active intermediate alpha-acyl-N-sulfonyl ketenimine without the need for a base.
Article
Chemistry, Multidisciplinary
Rong-De He, Yunfei Bai, Guan-Yu Han, Zhen-Zhen Zhao, Xiaobo Pang, Xiaobo Pan, Xue-Yuan Liu, Xing-Zhong Shu
Summary: This study successfully reported a cross-electrophile reaction of alkenyl acetates with alkyl bromides, establishing a new method for the synthesis of aliphatic alkenes that can add more structural complexity and molecular diversity with enhanced functionality tolerance. Preliminary mechanistic studies suggest that the Ni-I species plays a crucial role in the coupling of these two reactivity-mismatched electrophiles.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Guang-Li Xu, Chun-Yan Liu, Xiaobo Pang, Xue-Yuan Liu, Xing-Zhong Shu
Summary: A nickel-catalyzed reductive vinyl-vinyl coupling reaction has been developed, allowing the synthesis of dienylboronates with high structural complexity and molecular diversity. The reaction demonstrates broad substrate scope and can be conducted under mild conditions, highlighting its synthetic utility.
Review
Chemistry, Multidisciplinary
Xiaobo Pang, Pei-Feng Su, Xing-Zhong Shu
Summary: Transition-metal-catalyzed reductive coupling of electrophiles is a powerful method for constructing molecules. This review summarizes recent research in our laboratory on this topic, focusing on reactions involving readily available, low-cost, stable but unreactive electrophiles. The findings include deoxygenative C-C coupling of alcohols, reductive alkylation of alkenyl acetates, reductive C-Si coupling of chlorosilanes, and reductive C-Ge coupling of chlorogermanes.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Xue-Gong Jia, Qi-Wei Yao, Xing-Zhong Shu
Summary: This study reports a novel N-cyclization-alkylation reaction, showcasing the potential of heterocyclization for accessing enantioenriched cyclic architectures and solving a long-standing challenge in synthetic chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Qiu-Quan Pan, Liangliang Qi, Xiaobo Pang, Xing-Zhong Shu
Summary: Catalytic, three-component, cross-electrophile reactions have been applied to conjugated dienes and silicon chemistry, leading to the silylative difunctionalization of 1,3-dienes with chlorosilanes and aryl bromides under mild conditions. The reaction affords 1,2-linear-silylated products with a different selectivity compared to conventional methods. Preliminary mechanistic studies suggest that chlorosilane reacts with 1,3-diene first, followed by coupling with aryl bromide.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Xiaobo Pang, Xing-Zhong Shu
Summary: This Concept article summarizes the recent advance in nickel-catalyzed reductive C-Si couplings of chlorosilanes. This strategy allows chlorosilanes to be coupled with various carbon electrophiles under mild conditions, leading to organosilanes with improved molecular diversity, structural complexity, and functional group compatibility.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Multidisciplinary
Xiaobo Pang, Xing-Zhong Shu
Summary: Alcohols are readily available functionalities and their catalytic deoxygenative functionalization is highly attractive in organic synthesis. Transition metals, such as titanium and nickel, have been found to have unique reactivity in cleaving C-OH bonds and catalyzing C-C coupling reactions. Recent advances have led to improved reaction efficiency and expanded substrate scope, with the use of cobalt and copper catalysts showing new reactivity and selectivity issues.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Organic
Quan Lin, Weiqi Tong, Yunrong Chen, Xing-Zhong Shu
Summary: This study reports a Ti-catalyzed direct dehydroxylation of tertiary aliphatic alcohols under mild reaction conditions, resulting in the formation of Barton-type deoxygenation products. The method is tolerant to a wide range of functional groups, including primary alkyl chloride and carbonyl groups. It allows for selective dehydroxylation of tertiary alcohols in diols and the formation of deuterated products with moderate deuterium incorporation. The efficient modification of several drugs and natural products highlights the synthetic utility of this method.
Review
Chemistry, Organic
Ying-Hui Yang, Xiaobo Pang, Xing-Zhong Shu
Summary: Chlorosilanes are essential feedstock chemicals in the organosilicon world and the cross-coupling involving chlorosilanes by transition metal catalysis offers a promising way for producing organosilanes that play crucial roles in various research areas. This chemistry has been extended to different reactions, such as silyl-Heck reaction with alkenes and cross-electrophile coupling of chlorosilanes.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Liangliang Qi, Qiu-Quan Pan, Xiao-Xue Wei, Xiaobo Pang, Zitong Liu, Xing-Zhong Shu
Summary: Transition-metal-catalyzed sila-cycloaddition has been limited to specific sila-synthons, but this study demonstrates the potential of reductive nickel catalysis for using chlorosilanes as industrial feedstock chemicals. The reaction extends reductive coupling from carbocycle to silacarbocycle synthesis and from C-Si bond formation to sila-cycloaddition reactions. It offers a mild and versatile approach to access silacyclopent-3-enes and spirosilacarbocycles, with demonstrated optical properties and structural variations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Ming-Xiang You, Pei-Feng Su, Ze-Hui She, Xing-Zhong Shu
Summary: The C-Ge cross-coupling is a promising method for the precise synthesis of organogermanes. This study demonstrates the possibility of converting low-cost and easily available ester groups into organogermanes through cleavage of stable C-O bonds. The coupling of primary, secondary, and even tertiary benzylic pivalates with chlorogermanes is achieved under mild conditions. The scalability of the reaction and the derivatization of the formed benzylgermanes are also demonstrated.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Physical
Guan-Yu Han, Pei-Feng Su, Qiu-Quan Pan, Xue-Yuan Liu, Xing-Zhong Shu
Summary: In this study, non-radical precursors were used for enantioconvergent reactions through the utilization of Ni-C bond homolysis. The reductive germylation of non-redox-active alcohol derivatives enabled the stereoconvergent coupling of propargylic esters with electrophiles, demonstrating good propargylic selectivity. This work also highlights the potential for the development of catalytic methods for the synthesis of enantioenriched organogermanes.
Review
Chemistry, Organic
Li Sida, Shu Xing-Zhong, Wu Lipeng
Summary: The transition metal-catalyzed hydroboration of alkenes and alkynes, especially with late-transition metals, is highly efficient in the production of boronate esters. However, the use of early-transition metals such as zirconium and titanium is limited. This review summarizes the development of zirconium and titanium mediated hydroboration of alkenes and alkynes, and discusses the research trends in this area.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Xuejing Peng, Jingxian Huang, Guan-Yu Han, Xing-Zhong Shu
Summary: In this manuscript, a dynamic kinetic cross-electrophile coupling reaction of benzylic alcohols with alkenyl triflates is reported. This method allows for the replacement of the alcohol group with an alkenyl functionality, resulting in versatile benzyl-substituted cyclic alkenes. The reaction is orthogonal to existing reductive coupling methodologies and tolerates various functional groups.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Review
Chemistry, Multidisciplinary
Xiaobo Pang, Pei-Feng Su, Xing-Zhong Shu
Summary: Transition-metal-catalyzed reductive coupling of electrophiles has become a powerful tool for constructing molecules. This article summarizes recent research findings in our laboratory, focusing on reactions involving more readily available, low-cost, and stable but unreactive electrophiles. These findings include deoxygenative C-C coupling of alcohols, reductive alkylation of alkenyl acetates, reductive C-Si coupling of chlorosilanes, and reductive C-Ge coupling of chlorogermanes.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
