Review
Chemistry, Multidisciplinary
Xue Zhang, Kun Zhao, Zhenhua Gu
Summary: Arising from restricted rotation in single bonds due to steric or electronic effects, atropisomerism is a fundamental category for molecules to exhibit their three-dimensional characters, particularly in axially chiral biaryl compounds. Despite the widespread occurrence of axially chiral skeletons in natural products and bioactive molecules, catalytic asymmetric methods for their synthesis face challenges in controlling stereoselectivity for highly sterically hindered variants. However, recent studies have shown successful direct asymmetric synthesis of biaryl atropisomers through transition metal catalysis, offering insights into the activation of substrates and changes in chemoselectivity through torsional strain-promoted ring-opening reactions.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Qiuchi Zhang, Xiaoping Xue, Biqiong Hong, Zhenhua Gu
Summary: A palladium-catalyzed enantioselective ring-opening/carbonylation reaction of cyclic diarylsulfonium salts is reported. The sulfonium salts exhibited higher reactivity compared to thioethers, allowing the reaction to be conducted under mild conditions (room temperature). The steric repulsion of non-hydrogen substituents adjacent to the axis induced distortion in cyclic diarylsulfonium salts, leading to a preference for breaking the exocyclic C-S bond in the ring-opening reaction.
Article
Chemistry, Organic
Jian Gu, Biqiong Hong, Xiaoping Xue, Junwei Xi, Zhenhua Gu
Summary: A palladium-catalyzed domino cyclization/ring-opening reaction has been reported between 8H-indeno[1,2-c]thiophen-8-ols and N-(2-bromophenyl)propiolamide derivatives. The reaction allows for a highly stereospecific transfer of point chirality to axial chirality, enabling the synthesis of molecules with two chiral axes from compounds with only one stereogenic center.
Article
Chemistry, Organic
Yohann Landrain, Gwilherm Evano
Summary: An efficient copper-catalyzed inter/intramolecular oxy/aminoarylation of gamma-hydroxy/aminoalkenes with diaryliodonium triflates is described. Activation of the arylating agents and the alkene with copper(II) triflate in dichloromethane leads to the formation of highly substituted tetrahydrofurans and pyrrolidines, depending on the nature of the internal nucleophile. The cyclization process is stereospecific and can also be extended to oxyalkynylation.
Article
Chemistry, Organic
Bangxiong Kang, Lu Wang, Xihu Sun, Hongjian Liu, Zhonglin Wen, Yanwei Ren, Chaorong Qi, Huanfeng Jiang
Summary: This study reports a copper-catalyzed ring opening reaction of carbon dioxide (CO2) with amines, leading to the synthesis of a range of axially chiral carbamates. The method offers mild conditions, broad substrate scope, and excellent enantioselectivity. The synthetic applications of the method were demonstrated through the modification of natural products and drug molecules, as well as the diverse transformations of the axially chiral products.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Taiki Mori, Koki Abe, Seiji Shirakawa
Summary: An efficient enantioselective synthesis of important pharmaceutical building blocks called gamma-chiral alpha-spiro-gamma-lactones was achieved through a catalytic bromo-lactonization reaction using BINOL-derived chiral bifunctional sulfide. This reaction is suitable for alpha-allyl carboxylic acids containing different structures. The resulting alpha-spiro-type bromolactonization product can be transformed to obtain optically active gamma-functionalized alpha-spiro-gamma-lactones. This catalytic system was also proven useful in the asymmetric synthesis of alpha,alpha-diaryl- and dialkyl-substituted gamma-lactones.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yaxing Wu, Chao Wu, Fei Wang, Chao Chen
Summary: A [2 + 2 + 1] annulation protocol has been developed for the modular synthesis of 2,4-disubstituted thiophenes/selenophenes, showing excellent regioselectivity. Catalyzed by copper salt, the reactions utilize elemental sulfur and selenium as the chalcogen source. Mechanistic studies indicate that the process is initiated by a trisulfur radical anion detected using EPR.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Zhiyuan Bao, Chao Chen
Summary: An efficient method for the synthesis of multi-substituted cyclic imides was developed using cyanoesters and diaryliodonium salts. This method involves a cascade of N-arylation-acylation and rearrangement reactions, producing the desired heterocycles in high yields. The method has a broad substrate scope, excellent functional group compatibility, and can be extended to fused cyclic imides.
CHINESE CHEMICAL LETTERS
(2023)
Article
Chemistry, Organic
Hairui Du, Tao Qin, Heye Zhou, Bin Liu
Summary: A ligand and base-free copper-catalyzed method has been developed for the synthesis of O-arylated pyrazolin-5ones from readily available reagents. This methodology exhibits broad substrate scope and tolerance towards a wide range of functional groups. Control experiments demonstrated that specific diaryliodonium salts notably enhance reactivity in the O-arylation process of pyrazolin-5-ones.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Simone Grosso, Marcelina Mlynczak, Gwilherm Evano, Olivier Riant
Summary: An efficient and unprecedented cross-coupling reaction between acylzirconocenes and diaryliodonium tetrafluoroborates is reported. This method utilizes acylzirconocenes, readily prepared starting materials, and a low pressure of in situ generated carbon monoxide to synthesize a variety of alkyl-aryl-ketones under simple copper cyanide catalysis, without the need for additional ligands.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Xue Zhang, Kun Zhao, Zhenhua Gu
Summary: This article discusses the catalytic asymmetric synthesis of biaryl atropisomers through ring-opening reactions. The studies show that torsional strain can promote ring-opening reactions and provide an efficient method for the preparation of ortho tetra-substituted biaryl atropisomers with high enantioselectivity.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Multidisciplinary
Avery J. To, Graham K. Murphy
Summary: In this study, it was discovered that cyclic diaryliodonium salts can act as effective Lewis-acidic halogen-bond donor catalysts in the Nazarov cyclization reaction.
NEW JOURNAL OF CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Anna N. Philippova, Daria V. Vorobyeva, Pavel S. Gribanov, Ivan A. Godovikov, Sergey N. Osipov
Summary: An efficient method for the selective preparation of trifluoromethyl-substituted azepin-2-carboxylates and their phosphorous analogues has been developed via Cu(I)-catalyzed tandem amination/cyclization reaction of functionalized allenynes with primary and secondary amines.
Article
Chemistry, Multidisciplinary
Jida Zhang, Xiaomei Feng, Taiyang Guo, Xuliang Han, Haodong Liu, Xiangye Li, Xin Wang, Hansheng Li, Xinjin Li
Summary: A mild and efficient copper-mediated trifluoromethylation method was developed for the synthesis of trifluoromethylated arenes using readily available fluoroform and diaryliodonium salts. The reaction showed excellent functional group tolerance and provided good yields. This approach enables the straightforward incorporation of CF3 group into complex molecules, which is important for drug discovery applications.
Article
Chemistry, Organic
Mohamed Elsherbini, Wesley J. Moran
Summary: Cyclic and acyclic diaryliodonium salts were synthesized efficiently without the need for chemical oxidants or generation of chemical waste, with yields ranging from very good to excellent. When scaled-up to 10 mmol, over four grams of product with purity above 95% were obtained in less than three hours, and the solvent mixture could be recycled multiple times with minimal reduction in yield.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Zenghui Ye, Hong Zhang, Na Chen, Yanqi Wu, Fengzhi Zhang
Article
Multidisciplinary Sciences
Zenghui Ye, Yanqi Wu, Na Chen, Hong Zhang, Kai Zhu, Mingruo Ding, Min Liu, Yong Li, Fengzhi Zhang
NATURE COMMUNICATIONS
(2020)
Article
Chemistry, Organic
Mingruo Ding, Wenkai Hua, Min Liu, Fengzhi Zhang
Article
Chemistry, Multidisciplinary
Hong Zhang, Zenghui Ye, Na Chen, Zhenkun Chen, Fengzhi Zhang
Summary: An electrochemical method using easily available hydrazones has been developed for the synthesis of 1H-indazoles. This metal- and oxidant-free protocol is compatible with various functional groups and can be carried out on a gram-scale under neutral and mild conditions. The method has been successfully applied to the efficient synthesis of anti-tumor compounds. Mechanism studies suggest the involvement of a radical pathway, with an important role played by HFIP.
Article
Chemistry, Organic
Zenghui Ye, Rongjin Zhu, Feng Wang, Haobin Jiang, Fengzhi Zhang
Summary: Atom- and step-economic oxo-azidation and oxo-hydroxyphthalimidation of styrenes were developed under mild electrolytic conditions, leading to efficient synthesis of valuable alpha-azido or hydroxyphthalimide aromatic ketones from readily available starting materials. Mechanism studies revealed two different pathways involved in these transformations.
Article
Chemistry, Organic
Zongqiang Song, Kai Zhu, Hongqiang Jiang, Hengfa Gong, Zenghui Ye, Fengzhi Zhang
Summary: A simple and novel method for the synthesis of 1,3-dioxepine-fused (tricyclic) bispyrazoles is described. The protocol involves O-alkylation and intramolecular oxidative biheteroaryl coupling under mild conditions. The synthesized compounds have potential applications in medicinal or material chemistry.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Linwei Zeng, Fengzhi Zhang, Sunliang Cui
Summary: A modular and practical click chemistry is developed for the atroposelective synthesis of 1-triazolyl-2-naphthylamines. This method involves a [3 + 2] cycloaddition reaction under Rh-catalysis to assemble various aromatic or aliphatic azides with 1-alkynyl-2-naphthylamines, resulting in valuable 1-triazolyl-2-naphthylamine scaffolds. This asymmetric click technology offers easily accessible starting materials, mild reaction conditions, facile scalability, and good enantioselectivity. The thermostability of the products highlights their great potential for applications, while the synthetic transformations further enhance the molecular diversity of atropisomers.
Article
Chemistry, Medicinal
Xiang Li, Lina Yin, Jing Liao, Jun Yang, Binhao Cai, Yiming Yu, Sijia Su, Zhiteng Du, Xiaobo Li, Ying Zhou, Pan Chen, Won-Jea Cho, Nipon Chattipakorn, Aleksandr V. Samorodov, Valentin N. Pavlov, Fengzhi Zhang, Guang Liang, Qidong Tang
Summary: A series of novel O-benzylcinnamic acid derivatives were designed and synthesized, and compound L26 showed the best anti-inflammatory activity, being 7-fold more active than CIN. Further experiments revealed that L26 targeted MD-2 protein and competed with LPS to bind to MD-2, resulting in inflammation inhibition. In vivo experiments demonstrated that high doses of L26 were safe and it exhibited optimal pharmacodynamic and pharmacokinetic characteristics, suggesting its potential as a treatment agent for ALI.
EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY
(2023)
Article
Chemistry, Organic
Min Liu, Haobin Jiang, Jiyuan Tang, Zenghui Ye, Fengzhi Zhang, Yanqi Wu
Summary: Here, a base-mediated, highly meta-selective O-arylation process of phenols and cyclic diaryliodonium salts without the use of transition metals is reported. This novel and practical method has been demonstrated to be useful for the synthesis of iodine-containing meta-functionalized biaryl ethers with a broad functional group tolerance and environmental friendliness. Diverse transformations of the products have been conducted to obtain various valuable functionalized biaryls. Preliminary mechanistic studies provide support for the proposed aryne generation mechanism.
Article
Chemistry, Organic
Zhenkun Chen, Fengzhi Zhang
Summary: The Catellani reaction is a palladium-catalyzed hydrocarbon-activated multicomponent tandem reaction that involves an aryl halide, an electrophilic coupling reagent, and a terminating reagent. Norbornenes serve as co-catalysts and play critical roles in this reaction. After more than two decades of development, the Catellani reaction has become a unique method for the synthesis of poly-functionalized aromatics from easily accessible starting materials, with advantages of cross-coupling and adjacent metallization, as well as excellent reactivity and wide applicability. This manuscript reviews the important advances in Catellani reactions over the last four years, providing valuable insights for researchers in this prosperous research area.
Article
Chemistry, Organic
Huaipu Yan, Jing-Ran Shan, Fengzhi Zhang, Yuqing Chen, Xinyi Zhang, Qian Liao, Erjun Hao, Lei Shi
Summary: A radical strategy using metal-hydride hydrogen atom transfer (MHAT) via photoredox cobalt and titanium dual catalysis is reported for alkene functionalization. The method achieves excellent regio- and diastereoselectivity.
Article
Chemistry, Multidisciplinary
Min Liu, Yong Qian, Yanqi Wu, Fengzhi Zhang
Summary: A multicomponent, environmentally friendly protocol has been developed to generate di-aryl dithiocarbamates from readily available thianthrenium salts. The reaction can be smoothly conducted using both aromatic and alkyl amines without the need for photocatalysts, transition-metal catalysts, or ligands. A novel photoactivated electron donor-acceptor complex is proposed as the key intermediate. This protocol offers a new approach towards di-aryl dithiocarbamates and shows promise for potential applications in pharmaceutical chemistry and sulfur chemistry.
Article
Chemistry, Multidisciplinary
Zhide Zhang, Yangling Deng, Ming Hou, Xiaojing Lai, Meng Guan, Fengzhi Zhang, Rui Qi, Guanyinsheng Qiu
Summary: This paper describes iron/photoredox dual-catalyzed acyl nitrene formation and its application in constructing various C-O bonds towards phthalides. The reaction starts from N-methoxyl-2-alkylbenzamides. Mechanistic studies suggest that the reaction involves iron nitrene-based hydrogen atom abstraction (HAA), radical-polar crossover, and O-nucleophilic S(N)1. Radical rebound, commonly observed in previous publications, is not observed in this reaction. This reaction represents the first example of acyl nitrene-based synthesis of phthalides and has potential applications in the synthesis of marketed medicines.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Linwei Zeng, Shuheng Xu, Sunliang Cui, Fengzhi Zhang
Summary: The multicomponent reaction described for the synthesis of beta-aminoxy amides offers various advantages such as readily available starting materials, high atom economy, mild reaction conditions, and easy scalability. Control reactions and a crossover experiment have provided insights into the possible mechanism of the reaction.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Review
Chemistry, Organic
Na Chen, Zenghui Ye, Fengzhi Zhang
Summary: Carboxylic acids are crucial components in medicinal molecules, natural products, and agrochemicals, as well as basic building blocks for organic synthesis. Organic electrochemistry, as an environmentally friendly and sustainable synthetic method, offers a promising alternative to traditional high-temperature, costly, and oxidant-heavy carboxylic acid group transformations.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
