Article
Chemistry, Organic
Xing Wang, Zhen-Yu Wang, Xu Zhang, Hui Xu, Hui-Xiong Dai
Summary: In this article, an efficient palladium-catalyzed silylation of aryl and alkenyl ketones via C-C bond cleavage and C-Si bond formation is reported. This protocol demonstrates high efficiency and broad substrate scope. Applications in the late-stage diversification of biologically important molecules further showcase the synthetic utility of this method.
Article
Chemistry, Inorganic & Nuclear
Yesmin Akter Rina, Joseph A. R. Schmidt
Summary: We report an attractive and efficient synthetic approach to form Si-N bonds via the heterodehydrocoupling of silanes and amines catalyzed by a lanthanum-based N,N-dimethylbenzylamine complex [La(DMBA)(3)]. This method allows for the formation of numerous silylamines in high efficiency and moderate-to-excellent yields under mild conditions.
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
Ling Ding, Yuxiu Liu, Kaikai Niu, Qingmin Wang
Summary: In this study, a new iron-catalyzed reaction method is reported to synthesize valuable silicon compounds through visible-light-induced alkynylation of hydrosilanes. The reaction conditions are mild and common metal catalysts are used.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Ying Chen, Fei Wang, Weidong Rao, Shusu Shen, Daopeng Sheng, Shun-Yi Wang
Summary: An efficient method for the copper-catalyzed ring-opening hydrolysis of silacyclobutanes to silanols was developed in this study. This strategy offers the advantages of friendly reaction conditions, simple operation, and good functional group compatibility. It also allows for the introduction of S-S bonds into organosilanol compounds in a single step. The successful gram scale synthesis demonstrates the potential of this protocol for practical industrial applications.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Shuai Liu, Frederic Robert, Yannick Landais
Summary: Dual Ni and Ir catalysis allows the visible-light-assisted synthesis of arylsilanes without the need for strong bases, high temperature, and air/moisture sensitive reagents, resulting in moderate to good yields.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Tingzhi Lin, Pengcheng Qian, Yan-En Wang, Mingjie Ou, Long Jiang, Chen Zhu, Yuchuan Xu, Dan Xiong, Jianyou Mao
Summary: A novel method for the efficient synthesis of heterocycle-containing silanes with good functional group tolerance has been developed, with scalability demonstrated. This method allows for the generation of a diverse array of aryl(2-pyridyl)-methyl silane derivatives in good to excellent yields.
Article
Chemistry, Organic
Wanyao Zheng, Yongjie Xu, Hang Luo, Yunhui Feng, Jinqiao Zhang, Luqing Lin
Summary: In this study, we have reported a light-promoted dual catalysis for arylsilylation of alkenes via radical-radical cross-coupling with various hydrosilanes. This method provides a simple and efficient way to prepare organosilicon compounds with a wide range of substrates and good tolerance towards functional groups under transition-metal- and chemical-oxidant-free conditions. Additionally, the arylsilylation of alkenes can also proceed via a possible electron donor-acceptor complex under exogenous photocatalyst-free conditions.
Article
Chemistry, Physical
Lanxiao Zhao, Xianghui Shi, Jianhua Cheng
Summary: This study demonstrated the catalytic regioselective C-H silylation of alkoxy-substituted benzene derivatives using a specific calcium complex, offering an efficient and direct method for synthesizing silyl-substituted aromatic ether derivatives while avoiding transition metal. Proposed calcium anisyl complexes were isolated and structurally characterized as catalytic reaction intermediates.
Article
Chemistry, Organic
Xiaoyu Wu, Guangni Ding, Wenkui Lu, Liqun Yang, Jingyang Wang, Yuxuan Zhang, Xiaomin Xie, Zhaoguo Zhang
Summary: A simple and effective nickel-based catalytic system was developed for the electrophilically activated hydrosilylation of terminal alkenes with primary silanes, showing exclusive anti-Markovnikov selectivity, broad functional group tolerance, and good scalability under mild reaction conditions. However, secondary and tertiary silanes are not suitable for this protocol. Mechanistic studies revealed that the homogeneous catalytic hydrosilylation process involves electrophilically activated Si-H bond without nickel hydride generation.
Article
Chemistry, Multidisciplinary
Xuanzi Fan, Muliang Zhang, Yuanjun Gao, Qi Zhou, Yanbin Zhang, Jiajia Yu, Wengang Xu, Jianming Yan, Haiwang Liu, Zhexuan Lei, Yan Chong Ter, Supphachok Chanmungkalakul, Yanwei Lum, Xiaogang Liu, Ganglong Cui, Jie Wu
Summary: Organosilanes play vital roles in modern society, finding wide applications in various fields including functional materials, organic synthesis, drug discovery, and life sciences. However, their synthesis is a challenging task, especially for heteroleptic substituted silicon reagents. This study demonstrates the efficient and selective functionalization of multihydrosilanes using neutral eosin Y as a direct HAT photocatalyst, enabling the synthesis of fully substituted silicon compounds. Through this strategy, diverse functionalization of hydrosilanes and selective monofunctionalization of di- and trihydrosilanes can be achieved.
Review
Chemistry, Organic
Long Zheng, Xiao-Xue Nie, Yichen Wu, Peng Wang
Summary: This Minireview summarizes the recent advances in the construction of Si-stereogenic silanes through the transition-metal-catalyzed C-H activation approach, showcasing their significant synthetic value.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Dongshun Ni, M. Kevin Brown
Summary: A Ni-catalyzed silylacylation of alkenes is introduced, providing rapid access to beta-silyl ketones by combining alkenes, CIZnSiR3, and acid chlorides. The method involves a catalytic intermediate of [Ni]-SiR3 complex, which is rare for three-component alkene functionalization. The synthetic utility of the products is demonstrated, along with detailed mechanistic descriptions.
Article
Chemistry, Multidisciplinary
Naofumi Hara, Nao Uemura, Yoshiaki Nakao
Summary: A C2-selective mono-silylation of various pyridines has been developed using a Rh-Al complex, where the site- and mono-selectivity are controlled by the coordination of pyridine to the Lewis-acidic Al center. A reaction mechanism is proposed based on the isolation of a (2-pyridyl)silylrhodium intermediate from several mechanistic studies.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Hyune-Jea Lee, Changmo Kwak, Dong-Pyo Kim, Heejin Kim
Summary: In this study, an atom-economic flow approach was developed for the selective and sequential mono-, di-, and tri-functionalizations of unactivated hydrosilanes using serial organolithium reactions catalyzed by earth-abundant metal compounds. The use of t-BuOK as a catalyst enabled rapid reactions of organolithiums with hydrosilanes, leading to efficient generation of functionalized organolithiums and their consecutive reactions with hydrosilanes under mild conditions. The integrated one-flow system allowed for precise reaction control and combinatorial functionalizations of trihydrosilane, providing various tetrasubstituted organosilane libraries.
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, Physical
Hao Xie, Sheng Wang, Yuquan Wang, Peng Guo, Xing-Zhong Shu
Summary: In this study, a Ti-catalyzed radical dehydroxylative vinylation reaction of tertiary alcohols was demonstrated, providing a method for the construction of vinylated all-carbon quaternary centers. The reaction exhibited mild conditions and excellent functional group tolerance.
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)
