Article
Chemistry, Applied
Haifeng Yu, Jian Mo, Xuemin Niu, Dashuang Luo, Guangbo Che
Summary: Switchable synthesis of 3-alkenyl succinimides and maleimides was achieved by adjusting reaction conditions. The Michael addition reaction of alpha-oxo ketene dithioacetals and maleimides using CH3SO3H in DCE at 120 degrees C resulted in 40-90% yields of 3-alkenyl succinimides. The oxidative cross-coupling reaction of alpha-oxo ketene dithioacetals with maleimides using Pd(OAc)(2) in DMF at 20 degrees C yielded 40-80% yields of 3-alkenyl maleimides. The method can be scaled up to gram scale without the need for directing groups on the substrates.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Chih-Yu Lin, Wan-Wen Huang, Ying-Ti Huang, Sandip Dhole, Indrajeet J. Barve, Chung-Ming Sun
Summary: In this study, a rhodium(III)-catalyzed controllable [4 + 1] and [4 + 2] annulation of N-aryl pyrazolones with maleimides was explored for the synthesis of spiro[pyrazolo[1,2-a]indazole-pyrrolidines] and fused pyrazolopyrrolo cinnolines. The selectivity of the products was achieved through time-dependent annulation. The [4 + 1] annulation reaction proceeded via sequential Rh(III)-catalyzed C-H alkenylation of N-aryl pyrazolone, followed by intramolecular spirocyclization via aza-Michael type addition to afford spiro[pyrazolo[1,2-a]indazole-pyrrolidine].
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Chih-Yu Lin, Wan -Wen Huang, Ying-Ti Huang, Sandip Dhole, Indrajeet J. Barve, Chung -Ming Sun
Summary: A rhodium(III)-catalyzed controllable [4 + 1] and [4 + 2] annulation reaction has been developed for the synthesis of spiro[pyrazolo[1,2-a]indazole-pyrrolidines] and fused pyrazolopyrrolo cinnolines. The product selectivity is achieved through time-dependent annulation. The [4 + 1] annulation reaction involves sequential Rh(III)-catalyzed C-H alkenylation of N-aryl pyrazolone, followed by an intramolecular spirocyclization via aza-Michael type addition to afford spiro[pyrazolo[1,2-a]indazole-pyrrolidine]. However, prolonged reaction time converts the in situ formed spiro[pyrazolo[1,2-a]indazole-pyrrolidine] into fused pyrazolopyrrolocinnoline through a strain-driven ring expansion.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Na Li, Bing Hu, Xinying Zhang, Xuesen Fan
Summary: A controlled and selective construction of spiro or fused heterocyclic scaffolds can be achieved through one-pot cascade reactions of 1-phenylpyrazolidinones with maleimides. The reactions involve C-H bond activation/functionalization, intramolecular cyclization, and traceless fusion of the pyrazolidinonyl unit to form succinimide spiro pyrazolo[1,2-a]pyrazolones or succinimide-fused pyrazolidinonylcinnolines. These protocols offer easily tunable selectivity, broad substrate scope, cost-effective and sustainable oxidant, excellent atom economy, and facile scalability.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zhenwei Lv, Yan Li, Erik V. Van der Eycken, Lingchao Cai, Liangliang Song
Summary: Here, we report a metal-free cascade cyclization reaction that constructs structurally novel polyheterocycles by utilizing a hypervalent iodine(III) reagent. Under ambient conditions, alkyne-tethered N-alkoxybenzamides undergo a 6-exo-dig cyclization/dearomatization process to generate diverse N-O fused spiro polyheterocycles in good to high yields. This method features short reaction times, broad substrate scope, easy handling, and shows promising antifungal activity against crop and forest pathogenic fungi.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Zhenwei Lv, Yan Li, Erik V. Van der Eycken, Lingchao Cai, Liangliang Song
Summary: In this study, a metal-free cascade cyclization method was developed for the construction of structurally novel polyheterocycles. The approach involves the use of a hypervalent iodine(iii) reagent and generates diverse N-O fused spiro polyheterocycles in high yields. The synthesized compounds exhibit good antifungal activity against crop and forest pathogenic fungi, with one compound showing superior performance compared to the positive control.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Youhao Wei, Zheng Wang, Kaifeng Wang, Jiang-Kai Qiu, Zhaoshan Wang, Haotian Li, Xiu Duan, Kai Guo, Xiaoguang Bao, Xinxin Wu
Summary: This study reports a copper-catalyzed allenic C(sp(2))-H cyanation with exceptional site-selectivity, addressing the challenge in synthetic chemistry of functionalizing allenic C(sp(2))-H bonds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Fang Wang, Qianting Zhou, Xinying Zhang, Xuesen Fan
Summary: A novel and efficient alpha-C(sp(3))-H alkenylation of cyclic amines with maleimides was presented, featuring readily available and structurally diverse substrates, a green and economical catalyst, a unique reaction pathway, mild reaction conditions, high efficiency, and excellent atom economy. This new reaction enriches the application of Fe(III)-catalyzed C(sp(3))-H activation and functionalization.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Gouranga Naskar, Masilamani Jeganmohan
Summary: This paper describes a palladium-catalyzed [3+2] annulation reaction of substituted benzoic acids with maleimides, leading to tricyclic heterocyclic molecules with a free carboxylic group in a highly atom- and step-economical manner. The reaction involves dual C-H bond activation, including C(sp(3))-H activation at the benzylic position and C(sp(2))-H bond activation at the meta position of substituted aromatics. The success of this protocol relies on the presence of an external ligand, MPAA. Additionally, decarboxylation and esterification of the free carboxylic acid group in the observed products were conducted.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Ying-Ti Huang, Indrajeet J. Barve, Yi-Ting Huang, Sandip Dhole, Wei-Jung Chiu, Chung-Ming Sun
Summary: A Rh(III)-catalyzed cascade C-H activation and cyclization reaction was reported for the synthesis of benzimidazole-fused isoquinolines and benzimidazole-spiro isoindoles. Selective formation of these products can be achieved by using unsubstituted and substituted benzimidazoles at different positions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Review
Chemistry, Physical
Feng Liu, Zhen Zhang, Hai-yan Diao, Zhang-jie Shi
Summary: Silver catalysts have shown remarkable performance in the direct functionalization of C-H bonds due to their extraordinary catalysis efficiency, reaction selectivity, and cost-effectiveness. This review summarizes the development of silver-mediated C(sp(2))-H bond functionalization in the past decade, categorizing it based on the type of newly formed bond and discussing the mechanisms, scope, and limitations of the reported references.
Article
Chemistry, Multidisciplinary
Matthew R. Lasky, Tolani K. Salvador, Sukrit Mukhopadhyay, Matthew S. Remy, Thomas P. Vaid, Melanie S. Sanford
Summary: This report describes the development of a photochemical method for C(sp(2))-H pyridination that leverages the photoexcitation of electron donor-acceptor (EDA) complexes. The reaction results in aryl radical cation intermediates that can be trapped with pyridine nucleophiles under aerobic conditions. This approach eliminates the need for an exogenous photocatalyst and is cost-effective.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Zhi-Hao You, Yan-Kai Liu
Summary: A novel [4+2] cyclization reaction was developed for the asymmetric synthesis of polycyclic compounds containing chromane and spirooxindole moieties. The reaction proceeded via intramolecular E1cB elimination and produced products with good yields (up to 84%) and excellent enantioselectivities (most 98 to >99% ee) using a chiral bifunctional thiourea-tertiary amine catalyst (1-5 mol%).
Article
Chemistry, Organic
Fengru Zhou, Liwei Zhou, Pengyang Jing, Mingjie Sun, Guobo Deng, Yun Liang, Yuan Yang
Summary: A palladium-catalyzed chemoselective decarboxylative annulation of aryl iodides with cyclic beta-bromoacrylic acids is developed for the construction of diverse fused and spiro polycycles. The reaction exhibits high selectivity and diversity by employing different substrates.
Article
Chemistry, Multidisciplinary
Qi Liu, Xuyi Liu, Yazhou Li, Yu Zhou, Linxiang Zhao, Xuewu Liang, Hong Liu
Summary: In this study, a substrate- and pH-controlled strategy mediated by Rh(III) catalyst was successfully employed to construct four novel types of complicated penta-spiro/fused-heterocyclic frameworks via C-H activation/[4+1] and [4+2] annulation cascades. The method exhibited mild reaction conditions, broad substrate scope, moderate to good yields, and valuable applications, leading to the generation of novel di-spiro-heterocyclic and multiple fused-heterocyclic products with unique structures for the first time. Moreover, the novel spiro[cyclohexane-indazolo[1,2-a]indazole] scaffold constructed by this method showed potent antitumor activity against various refractory solid tumors and hematological malignancies in vitro. Overall, this work provided new insights into the construction of complex and diverse multiple spiro/fused-heterocyclic systems and offered novel valuable lead compounds for antitumor drug discovery.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Chong Zhao, Chen Chen, Bei Hu, Wei Tong, Hui Liu, Bingwen Hu, Chao Li
Summary: This study discovers the close interplay between Mg displacement and the stability of lattice oxygen redox (LOR). The substantial difference in LOR stability between two closely related model materials, P2 and P3-NMMO, is shown to stem from the different evolution mechanisms between P-type and O-type layers, accompanied by different degrees of Mg displacement. Theoretical calculations confirm that out-of-plane Mg displacement is favorable for desodiated P3-NMMO and leads to noticeable O2 loss during LOR.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Physical
Fushan Geng, Guozhong Lu, Yuxin Liao, Ming Shen, Bingwen Hu
Summary: Real-time monitoring of lithium deposition on anodes is increasingly important in advanced anode technology. Electron paramagnetic resonance (EPR) is an effective and selective detection technology due to the skin effect. In this study, quantitative in situ 1D EPR imaging was conducted with a magnetic field gradient to achieve spatial resolution along the Li growth direction. The quantification of Li deposits was calibrated using a standard, and a processing method was presented to correct the integration of the Dysonian line from metallic Li. The comparison of Li deposition processes in two different electrolytes reveals that the electrolyte containing FEC additive results in larger dimensions of plated Li and more uniform stripping, leading to higher Coulombic efficiency.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Hui Liu, Chao Li, Chong Zhao, Wei Tong, Bingwen Hu
Summary: This study uses electron paramagnetic resonance (EPR) spectroscopy to uncover the oxidized oxygen states formed in Li-excess 3d transition metal oxide cathodes and finds the formation of molecular O-2. Contrary to conventional wisdom, the inhibition of out-of-plane cation migration does not prevent the formation of this molecule. Additionally, the reversibility of the local structural changes during oxygen redox depends on the inhibition of cation disorder rather than the specific formation of oxidized oxygen.
ENERGY STORAGE MATERIALS
(2022)
Article
Chemistry, Physical
Hui Feng, Qi Yang, Chao Li, Yang Lin, Haigang Liu, Nian Zhang, Bingwen Hu
Summary: The use of 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin (TAPP) and 5,10,15,20-tetrakis(4-aminophenyl)-porphyrin-Co(II) (Co-TAP) as redox mediators in Li-O2 batteries is effective for optimizing battery performance. Co-TAP, with the synergistic effects of a center metal atom and organic ligand, exhibits better oxygen reduction and evolution properties. The comprehensive study of discharge/charge processes and parasitic reactions reveals that TAPP affects the formation mechanism of Li2O2, while Co-TAP can transform the main discharge product into LiOH without additional water, thereby eliminating singlet oxygen (1O2) and mitigating parasitic reactions associated with 1O2.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Bo Cao, Yiwei Li, Mingjian Zhang, Ningyan Cheng, Ming Shen, Bingwen Hu, Jianyuan Li, Zhibo Li, Shenyang Xu, Wenguang Zhao, Ni Yang, Junliang Sun, Shixue Dou, Yang Ren, Haibiao Chen, Liang Yin, Feng Pan
Summary: This study comprehensively investigates the charge/discharge behaviors of a Li-rich cathode in a wide voltage window and successfully synthesizes a stable new cathode material through introducing aromatic Sb@Ni-6 superstructure units. The findings deepen the understanding of the structural stability of Li-rich cathodes in a wide voltage window and contribute to the development of high-energy-density and safe cathodes.
JOURNAL OF POWER SOURCES
(2022)
Article
Nanoscience & Nanotechnology
Yuxin Liao, Hui Feng, Qi Yang, Ming Shen, Yu Jiang, Chao Li, Chenxuan Zhao, Fushan Geng, Bingwen Hu
Summary: In this study, the effects of oxygen reactions on the distribution of Li ions in the transition metal (TM) and alkali metal (AM) layers for Na-ion batteries were explored using a layered P2-Na0.83Li0.12Ni0.22Mn0.66O2 cathode. It was found that cycling with oxygen-redox-activation-at-first-cycle (ORAFIC) method significantly improved the cycling stability compared to low-voltage (LV) cycling and high-voltage (HV) cycling. The ORAFIC method stabilized the crystal structure and Li ion distributions in the TM and AM layers, reducing Li-ion loss.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Chen Chen, Chong Zhao, Hui Liu, Xiang Wu, Bei Hu, Jingxin Li, Bingwen Hu, Chao Li
Summary: In this study, the close interplay between irreversible Zn migration and the inactivation of LOR for Na-O-Zn configuration in layered oxides was revealed. A Na2/3Zn0.18Ti0.10Mn0.72O2 cathode was designed to effectively prevent Zn migration and enhance LOR reversibility. The results demonstrated that stable LOR can be achieved by manipulating intralayer cation arrangements in the Na-O-Zn configuration.
Article
Chemistry, Physical
Ying Jiang, Guozhong Lu, Shinuo Kang, Fushan Geng, Bingwen Hu
Summary: This article investigates the difference between ultrathin lithium metal layers on Cu-CC under pressure-holding and non-pressure-holding conditions, and explores the impact of ultrathin lithium metal layers on electrochemical performance.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Multidisciplinary
Yuyi Zhang, Yuting Du, Qinghong Yuan, Chao Hang, Xiaolei Zhang, Bingwen Hu, Qingyuan Jin, Mengdi Chen
Summary: In this study, it was discovered that mixing 2-(2-hydroxyphenyl)-1H-benzimidazole (HPBI) molecules with zeolitic imidazolate framework-8 (ZIF-8) colloidal suspensions resulted in significantly enhanced fluorescence. Through various techniques, it was found that HPBI molecules adsorbed onto the surface of ZIF-8 particles coordinatively and electrostatically, forming a new type of fluorescence emitter. These emitters were distributed periodically on the outer surface of ZIF-8 particles, with fixed distances smaller than the excitation light wavelength, suggesting the possibility of triggering collective spontaneous emission.
Article
Chemistry, Multidisciplinary
Xiang Wu, Chen Chen, Chong Zhao, Hui Liu, Bei Hu, Jingxin Li, Chao Li, Bingwen Hu
Summary: A novel cathode material for sodium-ion batteries is designed, which activates reversible lattice oxygen redox and effectively suppresses non-lattice oxygen redox and structural distortions. This material exhibits high capacity and stable charge/discharge voltage curves.
Article
Chemistry, Physical
Xiang Wu, Hui Liu, Xiaobing Lou, Fushan Geng, Jingxin Li, Chao Li, Bingwen Hu
Summary: Layered lithium-rich (Li-rich) oxide cathodes with capacity contribution via oxygen redox have potential for high energy density in Li-ion batteries. The chemical states of oxidized oxygen in charged materials are under debate, including O(2- ), O-O dimer (O-2)(n-) (n > 0), molecular O-2, and oxygen p redox. Electron paramagnetic resonance (EPR) spectroscopy reveals that covalent interactions between 4d transition metal and oxygen can inhibit trapped molecular O-2 but not O-O dimer formation in Li-rich ruthenate compounds Li2Ru0.75Sn0.25O3 and Li2Ru0.5Sn0.5O3.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Shinuo Kang, Fushan Geng, Xiaobing Lou, Guozhong Lu, Yuxin Liao, Ming Shen, Bingwen Hu
Summary: In this study, the extreme fast charging performance of graphite anodes in electric vehicles is improved by adding fluoroethylene carbonate (FEC) into the electrolyte. The kinetic mechanism is elucidated through in situ nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) experiments. The results show that FEC enhances the Li-ion mobility in graphite and optimizes the Li plating behavior.
ACS APPLIED ENERGY MATERIALS
(2023)
Article
Chemistry, Physical
Nianrui Guo, Fushan Geng, Guozhong Lu, Xinbiao Jiang, Chao Li, Bingwen Hu, Ming Shen
Summary: Solid-state NMR is a vital tool for studying the structural evolution of cathodes in lithium-ion and sodium-ion batteries. A novel IR-pjMATPASS method is proposed to measure T-1 relaxation with site-specific resolution for paramagnetic solids. The method is applied to the characterization of a ball-milling induced phase transition in Li6CoO4. The study provides a quantitative strategy for NMR studies of paramagnetic solids.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Yuxin Liao, Fushan Geng, Yu Jiang, Ming Shen, Bingwen Hu
Summary: This study finds that Na3V1.5Cr0.5(PO4)(3) exhibits improved performance in low temperature environments, reducing V-ion dissolution and maintaining V3+/V4+ redox reactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yuyi Zhang, Wei Zhang, Yajie Bian, Yiting Liu, Xiaolei Zhang, Mengdi Chen, Bingwen Hu, Qingyuan Jin
Summary: This study demonstrates the versatility of ZIF-8 as a carrier material for small molecule capture and fluorescence enhancement. The results indicate that the luminescent behavior of ZIF-8 changes when combined with HPBI, and the fluorescence enhancement effect varies with different concentrations of HPBI. The findings suggest that ZIF-8 may offer great promise for molecular fluorescence sensing.
