Article
Chemistry, Multidisciplinary
Huanhuan Cui, Changhao Niu, Mimi Xing, Chun Zhang
Summary: A novel NiH-catalyzed highly regioselective coupling of alkenes with vinyl chlorosilanes, constructing C-Si bonds, has been developed. This reaction allows for the synthesis of benzyl organosilanes with various functional groups, which can serve as versatile precursors for preparing complicated organosilicon compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yi Wan, Yumo Zhao, Jiajie Zhu, Qiyang Yuan, Wei Wang, Yongqiang Zhang
Summary: A metal-free catalytic approach for silyl transfer of silylboranes has been developed using a visible light-induced organophotocatalytic strategy. The protocol allows for the formation of various types of C-Si bonds by slightly adjusting the reaction conditions. This technology can also be applied to the construction of C-B, C-S, and C-Sn bonds, providing a versatile platform for bond activation and connection of main group elements. The green aspect of the reaction has been demonstrated by using Brij-30/water as a reaction solvent or sunlight as an alternative energy source.
Article
Chemistry, Multidisciplinary
Shuyou Chen, Jiefeng Zhu, Jie Ke, Yingzi Li, Chuan He
Summary: In this study, we report a new method for the synthesis of acyclic silanes bearing a silicon-stereogenic center using a rhodium-catalyzed intermolecular dehydrogenative Si-H/C-H cross-coupling reaction. The method shows good yields and stereo-control, significantly enlarging the chemical space of optically active silicon-stereogenic monohydrosilanes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo, Yan-Cheng Hu, Boshun Wan, Qing-An Chen
Summary: Transition metal catalyzed decarbonylation offers a unique synthetic strategy for new chemical bond formation. The study developed a visible light induced rhodium catalysis for decarbonylative coupling of imides with alkynes under ambient conditions, revealing the rhodium complex serves as both the catalytic center and photosensitizer. This visible light promoted catalytic decarbonylation strategy opens up new opportunities for re-evaluating old transformations with ligand dissociation as a rate-determining step.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Xu Wang, Shuai-Shuai Huang, Feng-Jiao Zhang, Jia-Le Xie, Zhao Li, Zheng Xu, Fei Ye, Li-Wen Xu
Summary: This study reveals a new method for introducing a silicon center on complex molecules, with high yields achieved through the cooperative catalysis of rhodium and copper. The synthesis of a variety of silicon-containing compounds was successfully achieved through the Rh/Cu co-catalyzed reaction.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Multidisciplinary
Zhen-Zhen Zhao, Xiaobo Pang, Xiao-Xue Wei, Xue-Yuan Liu, Xing-Zhong Shu
Summary: We report a new method for synthesizing organohydrosilanes from phenols and ketones. This method involves unconventional Si-Cl cleavage and offers a complementary scope to established methods. It can successfully couple aryl- and alkenylhydrosilanes with various electrophiles, and is tolerant of different functional groups. The method has demonstrated gram-scale reactions, incorporation of organohydrosilanes into biologically active molecules, and derivatization of the formed products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Qi-Chao Gan, Zi-Qi Song, Chen-Ho Tung, Li-Zhu Wu
Summary: This paper reports the first example of C(sp)-H/Si-H cross-coupling by photocatalysis. A series of alkynylsilanes are prepared in good to excellent yields using cheap and readily available starting materials and visible-light irradiation of CuCl and alkynes with silane. The potential of this transformation in practical organic synthesis of alkynylsilane intermediates is shown through large scale reactions with flow chemistry and late-stage functionalization of natural products.
Letter
Chemistry, Organic
Yumo Zhao, Yi Wan, Qiyang Yuan, Jinlian Wei, Yongqiang Zhang
Summary: A visible-light-induced photocatalytic C-Si formation strategy was developed using Martin's spirosilane-derived pentacoordinate silylsilicates as silyl radical precursors. The strategy exhibited efficient hydrosilylation of a wide range of alkenes and alkynes, as well as C-H silylation of heteroarenes. Notably, Martin's spirosilane was stable and could be easily recovered. Moreover, the reaction performed well using water as the solvent or low-energy green LEDs as an alternative energy source.
Article
Multidisciplinary Sciences
Jakub Szyling, Jedrzej Walkowiak, Agnieszka Czapik, Adrian Franczyk
Summary: A selective method for synthesizing unsymmetrically functionalized disiloxanes was developed, involving the hydrosilylation of internal alkynes followed by the hydrosilylation of alkynes or 1,3-diynes with 1,1,3,3-tetramethyldisiloxane. This strategy allowed the preparation of a new family of disubstituted disiloxanes that were previously inaccessible by other synthetic methods. Symmetrically functionalized disiloxanes were also obtained by directly hydrosilylating terminal or internal alkynes, demonstrating the versatility of the hydrosilylation process. The characterized compounds have the potential to be used as building blocks or coupling agents.
SCIENTIFIC REPORTS
(2023)
Article
Chemistry, Organic
Huiwei Xu, Wanyao Zheng, Wen-Deng Liu, Yuqiao Zhou, Luqing Lin, Jiannan Zhao
Summary: The construction of silicon-containing molecules has received attention in recent years. In this study, silyl radicals were generated through NHC catalysis under mild reaction conditions. This methodology offers a convenient route to a diverse range of β-silyl ketones with good functional group compatibility. The use of radical clock and electrochemical studies supports the hypothesis of ground-state SET, and a plausible mechanism for the organocatalytic transformation is proposed.
Article
Chemistry, Organic
Xiao-Hua Zhou, Xiao-Jun Fang, Fang-Ying Ling, Zheng Xu, Li-Quan Hong, Fei Ye, Li-Wen Xu
Summary: This article reports a catalytic system that enables cross-coupling reactions between alkynyl bromides and hydrosilanes via silicon-carbon bond formation. The synthesis of alkynylsilanes using this method is highly efficient and selective.
ORGANIC CHEMISTRY FRONTIERS
(2022)
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, Organic
Wei-Ke Zhu, Hua-Jie Zhu, Xiao-Jun Fang, Fei Ye, Jian Cao, Zheng Xu, Li-Wen Xu
Summary: In this study, we report the first rhodium-catalyzed hydrolytic cleavage of the silicon-carbon bond in silacyclobutanes using water as the reactant. A range of silacyclobutanes can be utilized in this reaction with the presence of Rh/BINAP complex, yielding the corresponding silanols in good yields. Moreover, a chiral ligand derived from 1,1,4,4-tetraaryl-2,3-O-isopropylidene-l-threitol-derived phosphoramidite can be employed to obtain Si-stereogenic silanol with promising enantioselectivity.
Article
Chemistry, Organic
Qi-Liang Yang, Yi-Rui Luo, Rong-Yi Xu, Bei-Ning Zhang, Yan-Ni Zhang, Hai-Ming Guo
Summary: A sustainable pathway for the synthesis of tetracyclic purinium salts via ruthenium-catalyzed electro-oxidative annulation of C-6-arylpurine nucleosides with alkynes without a stoichiometric metal oxidant has been developed. The protocol exhibits high regioselectivity, broad scope, and wide functional group tolerance, allowing efficient coupling of various biologically important molecules. A novel purinoisoquinolinium-coordinated ruthenium(0) sandwich intermediate has been isolated, crystallographically characterized, and electrochemically analyzed, offering direct mechanistic insight.
Article
Chemistry, Multidisciplinary
Tao He, Bin Li, Lichuan Liu, Wenpeng Ma, Wei He
Summary: The signature reactivity of silacyclobutane (SCB) is their cycloaddition reactions with various pi bonds. Recently, the first cases were disclosed where SCBs reacted with both C-sp2-H and C-sp3-H sigma bonds in an intramolecular fashion. It is reported that SCB is also an efficient reagent for C-sp-H bond silylation, with rhodium-catalyzed intermolecular reactions between SCBs and terminal alkynes producing a series of symmetrical and unsymmetrical tetraorganosilicons bearing a C-sp-Si functionality. Preliminary studies suggested that the reaction did not involve a cycloaddition pathway, but instead a direct activation of C-sp-H bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Wen-Qiang Cai, Qi Wei, Qing-Wei Zhang
Summary: The nickel-catalyzed benzylic substitution reaction of secondary phosphine oxide was described, providing dialkylated P-stereogenic tertiary phosphine oxides with high to excellent enantioselectivities. The reaction was performed under mild conditions using commercially available benzyl chlorides and bench-stable secondary phosphine oxides, and exhibited broad functional group tolerance. This work represents a practical example for the preparation of P-stereogenic phosphine compounds.
Article
Chemistry, Multidisciplinary
Tao He, Zheng-Wang Qu, Hendrik F. T. Klare, Stefan Grimme, Martin Oestreich
Summary: A regioselective addition reaction of unactivated, terminal alkenes has been reported using alkynylsilanes as the reagent. The reaction is initiated by the capture of a sterically unhindered silylium ion by a silylated phenylacetylene derivative, forming a bis(silylated) ketene-like carbocation. This key intermediate acts as the actual catalyst and undergoes a series of electrophilic addition reactions to maintain the catalytic cycle. The reaction mechanism is consistent with experimental findings and provides an atom-economical method for forming C(sp(3))-C(sp) and C(sp(3))-Si bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Tao He, Hendrik F. T. Klare, Martin Oestreich
Summary: Superelectrophilic silylium/arenium ions are effective in exhaustivedeuteration of electron-deficient aryl halides. Using inexpensive C6D6as the deuterium source, excellent degrees of deuteriumincorporation were achieved under ambient conditions. This method allows the preparation of expensive or noncommercially available NMR solvents.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Zhenqiang Chen, Yingying Sun, Shoufeng Wang, Qing-Wei Zhang
Summary: A base-promoted tandem Michael addition of malonates to 2,3-bis(diarylphosphinyl)-1,3-butadienes was developed for the synthesis of cyclopentyl 1,2-bisphosphine compounds. This method enables rapid construction of various 1,2-bis(diarylphosphinyl)cyclopentanes, and features readily accessible reactants, mild conditions and good functional group tolerance. The product could be easily transformed to the corresponding transition metal complexes, which may find broad applications in asymmetric catalysis.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Mechanics
Yu-fang Zheng, De-yong Qu, Li-chuan Liu, Chang-ping Chen
Summary: In this study, a nonlinear bending model of the nonlocal three-layer magneto-electro-elastic (MEE) laminated nanobeam resting on elastic foundation is established using Reddy's third-order shear deformation theory (RTSDT) and nonlocal elasticity theory. The model considers the geometrically nonlinear equations proposed by von Karman and also takes into account the effects of electric and magnetic potentials in the laminated nanobeam through Maxwell's magnetic-electro equations and boundary conditions. The governing equations are re-expressed in a dimensionless form and simplified using the Galerkin method. The study explores the effects of foundation parameters, nonlocal parameter, stacking sequence, external electric voltage and external magnetic potential on the bending behaviors of MEE laminated nanobeams.
INTERNATIONAL JOURNAL OF NON-LINEAR MECHANICS
(2023)
Article
Chemistry, Multidisciplinary
Tao He, Hendrik F. T. Klare, Martin Oestreich
Summary: The method of methylation of various arenes with methanol is disclosed. The reaction is initiated by counteranion-stabilized silylium or arenium ions, which form Meerwein's salt-like oxonium ions with methanol as the active methylating agents. The silylated methyloxonium ions are stronger electrophiles than their protonated congeners, allowing the Friedel-Crafts alkylation to proceed more efficiently and at a lower reaction temperature. The regeneration of these superelectrophiles within the catalytic cycle is accomplished by the addition of a tetraorganosilane additive, that releases a silylium ion through protodesilylation by the Bri nsted acidic Wheland intermediate, thereby acting as a productive proton-into-silylium ion generator. By this method, even the C-H methylation of electronically deactivated aryl halides with methanol is achieved. The protocol is also applicable to nonactivated primary as well as pi-activated benzylic alcohols. Dialkyl ethers are also competent alkylating agents in the presence of the quaternary phenylsilane additive.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Bin Zhang, Wen-Qing Zhou, Xu-Teng Liu, Yingying Sun, Qing-Wei Zhang
Summary: We report an efficient method for the synthesis of P-stereogenic alkynylphosphines with high enantioselectivity via a Ni-catalyzed asymmetric cross-coupling reaction, providing a new approach to the derivatization of phosphine compounds.
Article
Engineering, Multidisciplinary
Yu-fang Zheng, Li-Chuan Liu, De-yong Qu, Chang-ping Chen
Summary: This article presents the nonlinear postbuckling behavior of magneto-electro-thermo-elastic (METE) laminated microbeams. Based on the modified couple stress theory and Reddy's three-order shear deformation theory, along with the von Karman geometric nonlinearity, the nonlinear static model of METE laminated microbeam is established. The nonlinear governing equations and boundary conditions are derived using the principle of virtual work principle. An analytical method is then used to describe the nonlinear postbuckling behavior of METE laminated microbeam with simple supported and clamped boundary conditions. Numerical examples are provided to reveal the effects of various parameters on the critical buckling load and postbuckling response, as well as the distribution of magneto-electric potential through the thickness direction of the microbeam with different lay-up modes.
APPLIED MATHEMATICAL MODELLING
(2023)
Article
Chemistry, Organic
Bin Zhang, Xiao-Ming Zhang, Qing-Wei Zhang
Summary: Phosphine oxides and spirocyclic compounds are privileged molecules that are widely used in catalytic transformations as chiral ligands or bifunctional organocatalysts. In this study, a Pd-catalysed cross-coupling reaction was developed to synthesize spirocyclic amino-phosphine oxides with a P-stereogenic center, which could potentially serve as P*(O), N-ligands or organocatalysts.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Qing Zhang, Ran-Ran Cui, Qing-Wei Zhang
Summary: An asymmetric arylation of H-phosphinates with aromatic iodo or bromo compounds, catalyzed by cheap and easily available nickel(II) salts, allows the synthesis of P-stereogenic phosphinates. This method offers mild reaction conditions and good functional-group compatibility including aniline and phenol derivatives.
Article
Chemistry, Physical
Wei-Han Wang, Yue Wu, Peng-Jia Qi, Qing-Wei Zhang
Summary: A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was achieved using NiII catalysis. Alkenyl phosphine products with high selectivity were obtained and easily diversified into structurally diverse chiral phosphine compounds.
Article
Chemistry, Physical
Ya-Qian Zhang, Lingfei Hu, Liyan Yuwen, Gang Lu, Qing-Wei Zhang
Summary: A nickel-catalyzed hydrosulfenation reaction has been developed to efficiently synthesize enantioenriched sulfoxides, which have broad applications in drug synthesis and catalysis.
Article
Chemistry, Organic
Ranran Cui, Yinqi Wang, Liyan Yuwen, Li Gao, Zhuo Huang, Wei-Han Wang, Qing-Wei Zhang
Summary: In this study, a novel Ni(II)-catalyzed asymmetric C-P cross-coupling reaction is developed for the synthesis of valuable chiral heterocyclic tertiary phosphine oxides. The method is mild, efficient, and does not require an external reductant, light irradiation, or electricity.
Article
Chemistry, Organic
Zhuo Huang, Xu-Teng Liu, Ranran Cui, Qing-Wei Zhang
Summary: Activated vinylcyclopropanes can react with secondary phosphine oxides in the presence of nickel catalyst to form zwitterionic pi-allylmetal species. This asymmetric allylation reaction yields tertiary phosphine oxide products with high yields (up to 91%) and enantioselectivity (92% ee).
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ya-Qian Zhang, Xue-Yu Han, Yue Wu, Peng-Jia Qi, Qing Zhang, Qing-Wei Zhang
Summary: In this study, a highly regio- and enantioselective hydrophosphinylation reaction of secondary phosphine oxides and enynes was achieved through Ni catalysis. A new mechanism was discovered through kinetic studies and DFT calculations. The alkene moiety played a vital role in the reactivity, regio-, and enantioselectivity.
