Article
Chemistry, Organic
Lin Xiao, Xu-Ge Liu, Mei-Zhu Bao, Jia-Lin Song, Shao-Yong Chen, Yi-Chuan Zheng, Yan-Zhi Liu, Shang-Shi Zhang
Summary: The Cp*Rh(III)-catalyzed nitro-directed C-H alkylation/alkenylation of nitroarenes has been reported for the first time. This method exhibits high efficiency, broad substrate scope, and good functional group compatibility. Gram-scale experiments and synthetic applications confirmed the practicality of this method. Furthermore, preliminary mechanistic investigations consistently indicated that C-H bond cleavage is the rate-limiting step.
Article
Chemistry, Organic
Rohit Sarthi, Rohit Kumar, Tamanna Sharma, Upendra Sharma
Summary: In this study, a concise Rh(III)-catalyzed C(sp3)-H alkylation of 8-methylquinolines with oxabenzonorbornadiene scaffolds and other strained olefins was presented. The developed catalytic methodology exhibits key features such as the retention of the oxabenzonorbornadiene skeleton, broad substrate scope, and wide-ranging functional group tolerance. Mechanistic studies revealed that the reaction proceeds through a non-radical pathway, with the five membered rhodacycle serving as the key intermediate. This is the first report on the C(sp3)-H alkylation of 8-methylquinolines with strained oxabenzonorbornadiene scaffolds (with ring retention).
Article
Chemistry, Organic
Yuan He, Ting Zheng, Yin-Hui Huang, Lin Dong
Summary: In this study, a novel Rh(iii)-catalyzed olefination reaction using oxazole as a directing group has been realized, leading to the generation of diverse oxazole skeleton derivatives with long chain alkenyls in moderate to good yields. The reaction showed tolerance towards various functional groups, making it potentially valuable in the construction of diverse compounds.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Ankita Thakur, Ankit Kumar Dhiman, Sumit, Rakesh Kumar, Upendra Sharma
Summary: This research presents a Rh(III)-catalyzed selective C8-alkylation of quinoline N-oxides with maleimides and acrylates, showing good selectivity and substrate scope. The methodology was also demonstrated to be applicable for gram-scale synthesis and post-modification.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shuwen Zhao, Xiaojia Cai, Yuying Lu, Jinhui Hu, Zhuang Xiong, Jingwei Jin, Yin Li, Honggen Wang, Jia-Qiang Wu
Summary: A mild, selective, and redox-neutral C-H activation/annulation reaction of salicylaldehydes with fluorovinyl tosylates is reported. The use of monofluorovinyl tosylate leads to the synthesis of C2- and C3-substitution-free chromones, while difluorovinyl tosylate results in the construction of C2-fluoroalkoxy chromones. The reaction exhibits mild conditions and good functional-group tolerance.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Fei Zhao, Jin Qiao, Yangbin Lu, Xiaoning Zhang, Long Dai, Xin Gong, Hui Mao, Shiyao Lu, Xiaowei Wu, Siyu Liu
Summary: In this study, alkynylated imidazo[1,5-a]indoles and alpha,alpha-difluoromethylene tetrasubstituted alkenes were successfully synthesized via Rh(III)-catalyzed [4 + 1] annulation/alkyne moiety migration and C-H alkenylation/DG migration, showing excellent product selectivity, high yields, and good tolerance of functional groups.
Article
Chemistry, Multidisciplinary
Bidhan Ghosh, Satabdi Bera, Pintu Ghosh, Rajarshi Samanta
Summary: An efficient Rh(iii)-catalyzed strategy has been developed for the synthesis of quinoline braced cyclophane macrocycles via methyl (sp(3)) C-H functionalization, which is mild, simple, regioselective, and tolerates various functional groups with different ring sizes. The method involves C8-methyl metalation, metal-carbene formation, and migratory insertion, with high dilution not necessary and nitrogen being the only byproduct. Preliminary investigation suggests that the C-H metalation step is the rate-determining step.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Shrikant M. Khake, Ken Yamazaki, Yusuke Ano, Naoto Chatani
Summary: This study reports a branch-selective C-H alkenylation method using an iridium catalyst with alkenes, suitable for aniline derivatives containing a pyrimidine-directing group, offering a broad substrate scope and tolerating various functional groups. The origin of branch selectivity was investigated using density functional theory calculations.
Article
Chemistry, Multidisciplinary
Xin Xu, Chenguang Luo, Haoqiang Zhao, Yixiao Pan, Xin Zhang, Jiajie Li, Lijin Xu, Ming Lei, Patrick J. Walsh
Summary: A Cp*Rh(III)-catalyzed chelation-assisted direct C-H bond functionalization has been achieved, giving three different products from internal alkynes in controllable manner. These reaction manifolds offer a divergent access to valuable products with excellent regio- and stereoselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Anurag Singh, Rahul K. Shukla, Chandra M. R. Volla
Summary: In this study, a novel nonoxidative [5 + 1] annulation reaction was reported. By using Rh(III) catalyst, 2-alkenylanilides and allenyl acetate were selectively reacted to obtain 1,2-dihydroquinoline derivatives. The reaction involves a series of steps including activation, insertion, elimination, and cyclization, achieving the construction of compounds. The method has a wide range of applications and can be used for functionalization of natural products.
Article
Chemistry, Organic
Hui Xie, Jia-Lin Song, Chun-Yong Jiang, Yan-Xia Huang, Jun-Yi Zeng, Xu-Ge Liu, Shang-Shi Zhang, Fan Yang
Summary: This new method of thioether-directed acyloxylation of arenes through Cp*Rh(iii)-catalyzed C-H activation shows high functional group compatibility and broad substrate scope. Preliminary mechanistic studies have been conducted, proposing a tentative reaction mechanism for this novel process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Hui Xie, Mei Zhong, Xiao-Tong Wang, Jia-Qiang Wu, Yan-Qu Cai, Jidan Liu, Bing Shu, Tong Che, Shang-Shi Zhang
Summary: This study presents a novel method for the direct C(sp(2))-H amination of arenes using Cp*Ir(iii) and Cp*Rh(iii) catalysts with the assistance of a thioether directing group. The protocol is redox-neutral, has a broad substrate scope, high functional-group compatibility, and generates the desired products in moderate to excellent yields. This represents the first example of a thioether-directed Cp*Ir(iii) and Cp*Rh(iii)-catalyzed C(sp(2))-H amination reaction, and also demonstrates the use of azide compounds as a diversified and robust aminating reagent in thioether-directed C-H functionalization reactions.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Applied
Liming Zhang, Ru Zhao, Chunhui Liu, Zhaoyang Li, Jun-Long Niu, Hao-Ran Yang, Lijun Gao, Shuang-Liang Liu, Liming Zhou
Summary: The Rh(III)-catalyzed ortho alkylation of N-pyridylcarbazoles with nitroalkenes has been developed for the synthesis of a wide range of 2-(2nitroalkyl)carbazoles. Aromatic and aliphatic nitroalkenes both successfully participated in this alkylation reaction. The protocol also worked well with an indoline based substrate. Derivatization of the representative nitroalkane product was described.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Priyambada Prusty, Subramanian Jambu, Masilamani Jeganmohan
Summary: A mild, convenient, and effective Rh(III)-catalyzed site-selective C2-alkenylation of N-carboxamide indoles with unactivated alkenes at room temperature has been described. The reaction was successfully demonstrated with a variety of indole N-carboxamides and unfunctionalized/functionalized unactivated alkenes, and a possible reaction mechanism involving C-H activation/insertion/internal oxidation followed by protonation has been proposed and supported by deuterium-labeling studies.
Article
Chemistry, Organic
Hai-Shan Jin, Cai-Cai Liang
Summary: This study reports an efficient synthesis of isoindolinone-derived spiroisochromenes using a [3 + 3] annulation of 3-aryl-3-hydroxyisoindolinones. In this Rh(iii)-catalyzed spirocyclization reaction, vinylene carbonate acts as a three-atom synthon (C-C-O) through decarboxylation. This atom-economic reaction undergoes through a C-H activation pathway under mild conditions and represents the first example of using 3-aryl-3-hydroxyisoindolinones as building blocks for constructing spiroheterocycles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Qi-Kai Kang, Hang Shi
Summary: Introducing deuterium and tritium into molecules is crucial for drug discovery. Recent advancements in catalytic HIE reactions have provided efficient methods for late-stage labeling of bioactive complex molecules and pharmaceuticals, avoiding multistep syntheses.
Article
Chemistry, Multidisciplinary
Kai Chen, Qi-Kai Kang, Yuntong Li, Wen-Qiang Wu, Hui Zhu, Hang Shi
Summary: This study describes a rhodium-catalyzed amination of phenols, providing a concise method for the synthesis of diverse anilines with no byproduct. The use of an arenophilic rhodium catalyst enables the challenging keto-enol tautomerization of phenols and subsequent condensation with amines. The generality of this redox-neutral catalysis is demonstrated through reactions with various phenols and amines, showcasing the potential broad utility of the method, including late-stage functionalization of structurally complex bioactive molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Jia-Yue Li, Lun Li, Yun-Zhi Lin, Hang Shi
Summary: Allylic amines were synthesized through a nickel-catalyzed coupling reaction. The method is free of additional oxidant/reductant or activating reagent and avoids the use of external ligands, improving its atom economy.
SYNTHESIS-STUTTGART
(2022)
Article
Chemistry, Multidisciplinary
Yuntong Li, Wen-Qiang Wu, Hui Zhu, Qi-Kai Kang, Lun Xu, Hang Shi
Summary: In this study, we report Rh-catalyzed benzylic addition of alkylarenes to Michael acceptors, which involves the activation of the aromatic ring for deprotonation of the unactivated benzylic C-H bond and addition of the resulting carbanion to the α,β-unsaturated double bond. This byproduct-free method provides access to all-carbon quaternary centers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Xinyang Zhao, Jingyi Zhang, Wei Zhang, Zijian Guo, Wei Wei, Xiuxiu Wang, Jing Zhao
Summary: We report an Ir(III) complex, Ir1, containing a novel chiral pyridine RAS-selective lethal ligand (Py-RSL), that effectively inhibits GPX4 and FSP1 to induce ferroptosis in HT-1080 cells. Metal coordination endows Ir1 with fluorescent properties for real-time tracking and reduces the off-target toxicity of the Py-RSL ligand. Ir1 also inhibits the ErbB signaling pathway to enhance tumor suppression. This study provides a highly selective and efficient route to develop new ferroptosis-inducing metallodrugs.
Article
Chemistry, Multidisciplinary
Peiqing Sun, Kunlun Li, Xiao Liu, Jing Wang, Xusheng Qiu, Wei Wei, Jing Zhao
Summary: In this study, a biomimetic silver binding peptide AgBP2 was used to develop a simple synthesis method for biocompatible Ag2S quantum dots (QDs). The AgBP2 capped Ag2S QDs showed excellent fluorescence emission in the NIR-II window and exhibited physical and photostability in water. Under 808 nm NIR laser irradiation, AgBP2-Ag2S QDs acted as a photothermal agent for NIR photothermal conversion and a photocatalyst for generating reactive oxygen species (ROS). The obtained AgBP2-Ag2S QDs achieved a highly effective disinfection efficacy of 99.06% against Escherichia coli within 25 min of NIR irradiation, attributed to the synergistic effects of photogenerated ROS and hyperthermia. This work demonstrates a promising strategy for efficient bacterial disinfection.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jiang Su, Kai Chen, Qi-Kai Kang, Hang Shi
Summary: We describe a rhodium-catalyzed nucleophilic aromatic substitution of aryl chlorides or bromides with weakly nucleophilic hexafluoro-2-propanol. This method provides diverse hexafluoroisopropyl aryl ethers and relies on arene activation by means of ?(6)-coordination.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Multidisciplinary Sciences
Ke Li, Wen-Qiang Wu, Yunzhi Lin, Hang Shi
Summary: The authors demonstrate a relay strategy for constructing compounds with a chiral gem-diaryl carbon center through selective arene exchange and asymmetric hydrogenation. This strategy involves the selective arene exchange between 1,1-diarylethylenes or benzophenones with (naphthalene)Cr(CO)3, followed by asymmetric hydrogenation. Differentiating the prochiral faces of a double bond is challenging for hydrogenation catalysts.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Wen-Qiang Wu, Hang Shi
Summary: This review summarizes recent advances in the transition-metal-catalyzed dehydrogenative (3 + 2) annulation of aromatic hydrocarbons, which involves the fusion of two distinct components to construct 5-membered carbocycles through the dual functionalization of benzylic and ortho C-H bonds.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Xue Wu, Ding Li, Lei Xu, Yu-Fei Jiang, Yue Zhao, Jing Zhao
Summary: Recently, two novel Cd(II)-based metal-organic frameworks (MOFs) were synthesized and showed fluorescence sensing capacity for arginine, which has attracted considerable attention in the fields of nutrition analysis, health monitoring, and medical diagnosis. The structures of the complexes were found to have significant differences due to variations in the coordination modes and extension direction of the Cd-bib coordination complexes.
Article
Chemistry, Multidisciplinary
Yanyan Chen, Tingting Hao, Jing Wang, Yiming Chen, Xiuxiu Wang, Wei Wei, Jing Zhao, Yong Qian
Summary: A series of near-infrared fluorogenic probes were designed and synthesized for the rapid and selective detection of sphingosine. Through fluorescent imaging, the changes in sphingosine levels induced by A beta 42 oligomers and H2O2 were evaluated, and the distribution of sphingosine in living organisms was successfully mapped. This work provides a simple and efficient method for investigating the metabolic process of sphingosine and its connection to disease pathologies.
Article
Chemistry, Inorganic & Nuclear
Lu Zhu, Wenjing Du, Yanrong Li, Ding Li, Wei Wei, Jing Zhao, Xiuxiu Wang
Summary: In this study, two chiral Pt(II) metallacycles were designed and synthesized, and their antitumor activity was tested. The results showed that these two metallacycles exhibited strong cytotoxicity, especially against A549 cells. Mechanistic studies revealed that the metallacycles induced apoptotic cell death and immunogenic cell death, providing a new strategy for the development of immune-modulating platinum agents in cancer therapy.
INORGANIC CHEMISTRY
(2023)
Article
Nanoscience & Nanotechnology
Xiao-Mei Cheng, Peng Wang, Shi-Qing Wang, Jing Zhao, Wei -Yin Sun
Summary: This study demonstrates that depositing silver nanoparticles onto specific facets of NH2-MIL-125(Ti) can significantly enhance the activity and selectivity for photocatalytic CO2 reduction. The loaded Ag NPs led to a 2.2-fold increase in CO and a 16.2-fold increase in CH4 yields compared to the NH2-MIL-125(Ti) with exposed {111} facets. The introduction of Ag NPs also optimized the electronic structure of the photocatalyst and suppressed the recombination of photogenerated electron-hole pairs.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Aasim Saeed, Xiao-Yu Zhang, Zi-Qing Huang, Xin-Yang Zhao, Lei Xu, Yue Zhao, Wei-Yin Sun, Jing Zhao
Summary: In this study, two novel metal-organic frameworks (MOFs) were synthesized and their structures were analyzed. These complexes exhibited high catalytic activity and satisfactory reusability under mild conditions. These findings are significant for the application and catalytic field of MOFs.
Article
Chemistry, Multidisciplinary
Zi-Peng Chen, Ding Li, Lei Xu, Yu-Fei Jiang, Kai Lin, Yue Zhao, Jing Zhao
Summary: Cationic metal-organic frameworks (MOFs) have recently gained attention for their potential in treating wastewater containing toxic anions. In this study, two novel cationic MOFs were constructed using a neutral imidazole-containing ligand. The structures and properties of the MOFs were analyzed, and it was found that one of the MOFs exhibited high efficiency and recyclability in adsorbing Cr2O72-.
NEW JOURNAL OF CHEMISTRY
(2022)
