Review
Chemistry, Applied
Jacques Muzart
Summary: This article summarizes the influence of carboxylate ligands and carboxylic acids or alkali metal carboxylates additives on the efficiency of C-C bond formation under palladium catalysis, with a focus on their effects on domino diarylation and annelation reactions. Plausible reaction mechanisms and personal comments are provided whenever possible.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Yuri Saito, Jun Kikuchi, Chen Wang, Naohiko Yoshikai
Summary: We report the design and development of Co/Al and Co/Mg bimetallic catalysts supported by a phosphine/secondary phosphine oxide (PSPO) bifunctional ligand for the selective C-H alkenylation of nitrogen-containing heteroarenes with alkynes. These catalysts enable the alkenylation of pyridine, pyridone, and imidazo[1,2-a]pyridine derivatives at the C-H site proximal to the Lewis basic nitrogen or oxygen atom, with a selectivity profile distinct from previously developed cobalt-diphosphine/aluminum catalyst. The alkenylated products were obtained in moderate to good yields using various heterocycles and differently substituted internal alkynes. Kinetic isotope effect experiments suggest the irreversibility of the C-H activation step, the relevance of which to the rate-limiting step depends on the reaction conditions. Density functional theory calculations indicate that ligand-to-ligand hydrogen transfer is the common mechanism of C-H activation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Gayathri B. Gange, Amanda L. Humphries, Mark D. Smith, Dmitry V. Peryshkov
Summary: In this study, we report the reactivity of carboranyl diphosphine with terminal alkynes, resulting in the formation of boron-containing phosphacycles. The reaction combines the activation of electron-deficient alkynes by phosphine groups and the redox behavior of carborane clusters, leading to the formation of a fused product of alkenylphosphonium cycle and reduced carborane cluster.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Daigo Hayashi, Tomohiro Tsuda, Ryo Shintani
Summary: A palladium-catalyzed skeletal rearrangement has been developed to synthesize highly fused tetrahydrophenanthrosilole derivatives via bond exchange. The reaction conditions can be tuned to produce different products, fused dihydrodibenzosilepin derivatives.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Md. Emdadul Hoque, Jin-Quan Yu
Summary: In this study, we report a new method for the gamma-arylation and gamma-lactonization of aliphatic acids, enabled by a L,X-type CarboxPyridone ligand catalyzed Pd(II) reaction. A wide range of gamma-arylated gamma-lactones can be efficiently synthesized in a single step, and the arylated lactones can be further converted into disubstituted tetrahydrofurans, which are prominent scaffolds in bioactive molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hai Huang, Tianyu Zhang, Jianwei Sun
Summary: The use of soft carbon nucleophiles to open oxetanes has been developed for efficient C-C bond formation. Silyl ketene acetals and styrene-based carbon nucleophiles can generate a wide range of highly oxygenated molecules in the presence of catalysts, which are key substructures in natural products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Inorganic & Nuclear
Seiji Ogo, Takeshi Yatabe, Hidetaka Nakai
Summary: This review discusses whether the ligand design used in catalysts mimicking O2-tolerant [NiFe] hydrogenase can be applied to ligand design in catalysts for C-C bond forming reactions. It explores the possibility of applying the ligand design methodology in reductive C-C coupling and C-H arylation reactions.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Muhammad Asif Iqbal, Le Lu, Hina Mehmood, Ruimao Hua
Summary: This study reports a Cs2CO3-promoted cross-coupling reaction of arenes with cyano-/nitro-substituted aryl halides in DMSO to afford biaryls in the absence of ligands. The cyano/nitro groups in biaryls are shown to be useful for further transformations. Additionally, the formation of dibenzofurans from reactions between arenes and 1-bromo-2-iodobenzene is reported. A radical mechanism for the formation of biaryls is proposed based on control experiments and theoretical studies.
Article
Chemistry, Multidisciplinary
Chamila Manankandayalage, Daniel K. Unruh, Clemens Krempner
Summary: The intramolecular inverse frustrated Lewis pairs (FLPs) with weakly Lewis acidic boryl and strongly basic guanidino moieties were synthesized and characterized, demonstrating their capability to activate small molecules. These novel FLPs show promising potential in diverse chemical transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Hongwu Jiang, Kaiwen Li, Shuangfeng Dong, Zhuqi Chen, Guochuan Yin
Summary: Transition-metal-catalyzed oxidative C-H olefination/annulation reactions are attractive for constructing heterocyclic compounds. However, most syntheses require stoichiometric oxidants for satisfactory catalytic efficiencies. This study presents a Pd(II)/LA-catalyzed oxidative C-H olefination/annulation reaction using dioxygen balloon as the sole oxidant to synthesize dihydrophenanthridines, with LA significantly improving the catalytic efficiency of Pd(OAc)2. Mechanistic studies reveal that C-H activation by Pd(II) is reversible, and the incorporation of deuterium from solvent into the recycled substrate depends on the aromatic electronic effect of the substrates.
Article
Chemistry, Organic
Ganesh Pandey, Sandip Kumar Tiwari, Pushpendra Singh, Pradip Kumar Mondal
Summary: The photocatalytic regiospecific p-silylation of arenes has been achieved through the coupling of in situ generated silyl radical with arene radical cation. The p-silylated arenes can be further utilized for exclusive o-silylation reaction, regiospecific o-acylation, and o-alkylation reaction.
Article
Chemistry, Multidisciplinary
Guangrong Meng, Liang Hu, Martin Tomanik, Jin-Quan Yu
Summary: Pd-II-catalyzed beta- and gamma-C(sp(3))-H heteroarylation of free carboxylic acids using pyridine-pyridone ligands overcomes limitations in selective functionalization and compatibility with heteroatoms. A sequence of three consecutive C(sp(3))-H activation reactions of pivalic acid constructs diverse quaternary carbon centers containing heteroaryls, offering a valuable tool for breaking new ground in medicinal chemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhe Zhuang, Shuang Liu, Jin-Tang Cheng, Kap-Sun Yeung, Jennifer X. Qiao, Nicholas A. Meanwell, Jin-Quan Yu
Summary: In this study, a novel C-H functionalization reaction was reported, which utilizes common protecting groups and practical oxidants for the lactamization of tosyl-protected aliphatic amides. The reaction was enabled by a specific ligand and shows mild reaction conditions, good scalability, and the use of convenient oxidants and protecting groups. Further derivatization of the beta-lactam products allows the synthesis of various biologically significant compounds.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Zhe Zhuang, Alastair N. Herron, Jin-Quan Yu
Summary: The development of C(sp(3))-H functionalizations of free carboxylic acids has provided a wide range of versatile reactions, enabling convenient synthesis of cyclic anhydrides using Mo(CO)(6) as a solid CO source and a bidentate ligand. Succinic anhydride products serve as versatile intermediates for introducing various functional groups at the beta position of parent acids, offering a divergent strategy for synthesizing carboxylic acids inaccessible by previous beta-C-H activation reactions. Furthermore, enantioselective carbonylation of free cyclopropanecarboxylic acids has been achieved using a chiral bidentate thioether ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Qingmei Liu, Zhi Zhou, Minyao Kuang, Hui Gao, Wei Yi, Shengdong Wang
Summary: By utilizing a calcium(II)/hexafluoroisopropanol cocatalytic system, an efficient and practical coupling reaction between 3-aminobenzoic acids and alkynes has been achieved, resulting in the direct and regioselective access to the phthalide framework with good compatibility towards substrates and functional groups. Mechanistic studies have revealed an ortho-C-alkenylation/hydroacyloxylation cascade for this transformation.
Article
Chemistry, Medicinal
Sen Li, Meng Wang, Shengcong Chen, Maxwell Ampomah-Wireko, Chen Gao, Ziwei Xia, Lauraine Nininahazwe, Shangshang Qin, En Zhang
Summary: The development of bacterial resistance to conventional antibiotics has posed challenges in treating bacterial infections. In this study, a series of cationic compounds with different linkers were designed and synthesized, showing high antibacterial activity against Gram-negative and Gram-positive bacteria. The best compound, 3e, demonstrated excellent antibacterial activity and low hemolytic toxicity. Mechanism studies revealed its potential bactericidal mechanism and its ability to effectively reduce the load of methicillin-resistant Staphylococcus aureus (MRSA). These findings highlight the significance of divergent linkers in antimicrobial peptide mimetics for treating bacterial infections.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Ru-Xin Liu, Feng Xiong, Chao Chen, Tong-Mei Ding, Shu-Yu Zhang
Summary: Project-based learning is a widely used approach in organic laboratories, which enhances student-centered training by focusing on complex issues and real-world problems in chemistry. Here, we combined organic synthesis, electrochemistry, and green chemistry to improve students' understanding of organic reactions and mechanisms. The integration of green chemistry concepts resulted in substantial improvement in student comprehension. Through designing and conducting a simple electrochemical reactor, students successfully accomplished the synthesis of (+/-)-muscone. This comprehensive project, including literature review, experimental procedures, and essay writing, received highly positive feedback from students.
JOURNAL OF CHEMICAL EDUCATION
(2023)
Article
Chemistry, Physical
Pengshuai Zhang, Haiyan Luo, Lan Cui, Jixiu Deng, Shiyu Xie, Danfeng Liu, Shuqi Wang, Xiaoying Si, Zichao Wang, Yameng Wan, En Zhang, Xing Li, Lu Zhang
Summary: The solid-liquid equilibrium solubility of artemisinin (ART) Form I was determined in twelve mono-solvents using a laser dynamic method. The results showed that the minimum solubility of ART (Form I) was observed in n-propanol at 283.15 K, while the maximum mole fraction solubility was found in N,N-dimethylformamide at 323.15 K. The solubility behavior and thermodynamic properties were analyzed, and the molecular similarities and intermolecular interactions of ART (Form I) were investigated in the different solvents.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
Article
Chemistry, Organic
Jin Yin, Peng Chen, Le-Wei Miao, Jie Wang, Yi-Jun Jiang
Summary: This study demonstrated the first direct and selective 3,6-dithiolation and 3,6-diselenylation of carbazoles using diaryl disulfides/diselenide as the sulfur/selenium source. This simple, general, and efficient method can deliver a wide range of 3,6-disulfenyl-carbazoles and 3,6-diselenyl-carbazoles with high regioselectivity in a one-step reaction mediated by Ag/K2S2O8.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Thermodynamics
Pengshuai Zhang, Ruping Ge, Chunxia Jin, Jixiu Deng, Feiyang Dai, Yameng Wan, Beibei Zhang, Shuwei Yu, Xing Li, En Zhang, Lan Zhang, Lu Zhang
Summary: The mole fraction solubility of 1-HPE in twelve mono-solvent systems was determined, and various models were used to correlate its solubility. Furthermore, Hansen solubility parameters analysis and Hirshfeld surface analysis were performed, and thermodynamic properties were calculated.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2023)
Article
Chemistry, Medicinal
Hongtao Kong, Shangshang Qin, Dachao Yan, Boyuan Shen, Tingting Zhang, Meng Wang, Sen Li, Maxwell Ampomah-Wireko, Mengmeng Bai, En Zhang, Jianfeng Cai
Summary: A series of diamino acid compounds with aromatic nuclei linkers were designed and synthesized as potential antibacterial agents against MRSA. Compound 8j showed good activity against clinical MRSA isolates, low hemolytic toxicity, and the best selectivity against S. aureus. It was able to quickly kill bacteria without inducing resistance and achieve a significant reduction in MRSA count in a mouse infection model.
JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chao Chen, Shen-Yuan Zhang, Shuai-Xi Li, Zi-Ha Li, Ru-Xi Liu, Jun-Chen Kang, Tong-Mei Ding, Shu-Yu Zhang
Summary: In this study, a unconventional electroreductive fluoroalkylative heteroarylation is developed for the synthesis of perfluoroalkyl-containing organic molecules. This novel method combines electrochemistry with radical addition and remote heteroaryl migration, allowing the introduction of various heteroaryls and fluoroalkyls into products. Deuterium-labeling experiments and density functional theory calculations reveal the reaction mechanism and the role of N,N-dimethylformamide in providing hydrogen atoms for radical quenching. The migrated benzothiazole moiety can be further transformed into a formyl group, enabling the facile synthesis of substituted cyclopentanones.
CELL REPORTS PHYSICAL SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Ai-Fang Wang, Jin-Miao Tian, Xiao-Jing Zhao, Zi-Hao Li, Ye Zhang, Ka Lu, Hong Wang, Shu-Yu Zhang, Yong-Qiang Tu, Tong-Mei Ding, Yu-Yang Xie
Summary: An asymmetric intramolecular hydroalkylation of unactivated internal olefins with tethered cyclic ketones was achieved by the cooperative catalysis of a newly designed chiral amine (SPD-NH2) and Pd-II complex, offering a straightforward route to bridged or fused bicyclic systems containing three stereogenic centers with excellent enantioselectivity (up to 99% ee) and diastereoselectivity (up to >20:1 dr). The resulting bicyclic products could be easily converted into a diverse range of key structures commonly found in bioactive terpenes, such as ∆(6)-protoilludene, cracroson D, and vulgarisins. Density functional theory calculations revealed that the steric hindrance between the Ar group of the SPD-NH2 catalyst and the branched chain of the substrate, hydrogen-bonding interactions between the N-H of the enamine motif and the C=O of the directing group MQ, and the counterion of the Pd-II complex were identified as key factors for the excellent stereoinduction in this dual catalytic process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zhen-Bang Chen, Ru-Xin Liu, Zi-Hao Li, Tong-Mei Ding, He-Yuan Bai, Zengming Shen, Shu-Yu Zhang
Summary: An efficient palladium-catalyzed enantioselective direct N-alkylation reaction using a novel axially chiral styrene-phosphine ligand SJTU-PHOS-1 was developed. The reaction showed good functional group compatibility and a wide range of substrate scope under mild conditions. Furthermore, DFT calculations revealed the coordination mode of the metal catalyst and the axially chiral styrene-phosphine ligand in enantioselectivity control.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jun-Jie Yin, Yun-Peng Wang, Jun Xue, Feng-Fan Zhou, Xing-Qian Shan, Rong Zhu, Kun Fang, Lei Shi, Shu-Yu Zhang, Si-Hua Hou, Wujiong Xia, Yong-Qiang Tu
Summary: The first total syntheses of polycyclic diterpenes phomopsene (1), methyl phomopsenonate (2), and iso-phomopsene (3) have been achieved through an unusual cascade reorganization of C-C single bonds. This approach involves a synergistic Nazarov cyclization/double ring expansion for rapid and stereospecific construction of the tetraquinane scaffold, as well as a one-pot strategic ring expansion through Beckmann fragmentation/recombination to efficiently assemble the tetracyclic skeleton. The correct structure of iso-phomopsene was determined to be the C7 epimer of the originally assigned structure, and the absolute configurations of the target molecules were confirmed through enantioselective synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yu Hao, Zi-Hao Li, Peng-Fei Lian, Quan-Zhe Li, Yuan She, Zhi-Gang Ma, Shu-Yu Zhang
Summary: This study describes a stereoselective sulfa-Michael/aldol cyclization reaction using a novel axially chiral styrene-based organocatalyst. The reaction successfully produces highly substituted tetrahydrothiophenes with an alkyne-substituted quaternary stereogenic center. The reaction tolerates a wide range of alkynyl-substituted acrylamides and shows excellent asymmetric introduction, scalability, and product diversification.
Review
Chemistry, Physical
Zi-Hao Li, Quan-Zhe Li, He-Yuan Bai, Shu-Yu Zhang
Summary: Axially chiral molecules, a subclass of molecular chirality, are extensively used in chiral ligands and catalysts and exist in biologically active compounds. Atropisomeric styrenes, which have constrained rotation of the C(vinyl)-C(aryl) bond, have gained recent attention and numerous methods have been developed for their chemical preparation. This review discusses synthetic strategies and mechanistic studies of axially chiral styrenes, aiming to provide inspiration and advice for scientists interested in this topic.
Article
Chemistry, Multidisciplinary
Yu Hao, Zi-Hao Li, Zhi-Gang Ma, Ru-Xin Liu, Rui-Tian Ge, Quan-Zhe Li, Tong-Mei Ding, Shu-Yu Zhang
Summary: A novel axially chiral styrene-based organocatalyst with a pyrrole ring was designed and synthesized. This catalyst exhibited exceptional capabilities in producing densely substituted spirooxindoles with an alkyne-substituted quaternary stereogenic center via mild cascade Michael/cyclization reactions. The high conversion rates and exceptional enantioselectivity were attributed to the chiral matched pi-pi interactions and multiple H-bonds between the organocatalyst and substrates, as supported by experiments, X-ray structure analysis, and DFT calculations.
Article
Chemistry, Multidisciplinary
Feng Xiong, Ru-Xin Liu, Xiao-Xuan Fan, Min Zhang, Yuan She, Wei-Qing Cao, Chao Chen, Tong-Mei Ding, Shu-Yu Zhang
Summary: The demand for sustainable synthetic methods in modern industry is increasing, leading to the prominence of organic electrochemical synthesis. This laboratory experiment is designed to train undergraduates in understanding and learning the concepts and operations of organic electrochemistry. By evaluating sustainability through the 12 principles of Green Chemistry, students can focus on variables and sensitivities in experimental operations.
JOURNAL OF CHEMICAL EDUCATION
(2023)
Article
Polymer Science
Yunzhi Fang, Xiaojie He, Jun-Chen Kang, Le Wang, Tong-Mei Ding, Xuemin Lu, Shu-Yu Zhang, Qinghua Lu
Summary: A methyl regulation strategy is proposed and verified in this work to balance the optical and thermal properties of colorless polyimide films. The strategy involves the introduction and substitution of methyl side groups, which help improve transparency and heat resistance.
