Volume 36 Issue 12
24 December 2024
Yuan-Zheng Cheng, Muzi Li, Rui-Xiang Wang, Long-Hao Zhu, Wen-Jie Shen, Xin-Xuan Zou, Qing Gu, Shu-Li You. The Development and Perspective of Dearomatization Reaction[J]. Progress in Chemistry, 2024, 36(12): 1785-1829.
Representing an important class of ubiquitous chemical feedstock, aromatics have been extensively utilized in the nucleophilic aromatic substitution (SNAr) reactions, nitration reactions, Friedel-Crafts alkylation and acylation reactions, cross-coupling reactions, C-H bond functionalization reactions etc. Dearomatization reaction is another type of transformations of aromatics, in which their aromaticity is destroyed or reduced. Since its first report, dearomatization reaction has served as an efficient platform to create C(sp3)-H-rich spiro, fused and bridged polycyclic structures, widely applied in material and medicinal chemistry. In the past two decades, various dearomatization reactions have been established by using transition-metal catalysis, organocatalysis, enzymatic catalysis, photocatalysis, and electrocatalysis. Diverse polycyclic structures have been obtained by the dearomatization of indoles, pyrroles, (benzo)furans, (benzo)thiophenes, quinolines, pyridines, benzenes, naphthalenes, etc. The coupling reagents, including nucleophiles, electrophiles, dipoles, radicals, and carbenes have been developed to assemble different functional groups on dearomative framework. In this review, we briefly summarized the developed dearomatization reactions, which were categorized by the kinds of aromatic compounds. The remaining challenges and perspectives on the future development of dearomatization reactions are also included here.
1 Introduction
2 Indoles and pyrroles
2.1 Hydrogenation reactions
2.2 Oxidative dearomatization reactions
2.3 Dearomatization reactions with electrophiles
2.4 Dearomatization reactions with nucleophiles
2.5 Dearomatization reactions with radicals
3 Benzofurans and furans
3.1 Dearomatization reactions with nucleophiles
3.2 Dearomatization reactions with electrophiles
3.3 Dearomatization reactions with radicals
3.4 Cycloaddition dearomatization reactions
4 Benzothiophenes and thiophenes
4.1 Hydrogenation reactions
4.2 Dearomatization reactions with nucleophiles
4.3 Dearomatization reactions with electrophiles
4.4 Dearomatization reactions with radicals
4.5 Cycloaddition dearomatization reactions
4.6 Ring expansion dearomatization reactions
4.7 Dearomatization reactions with carbenes
5 Phenols and naphthols
5.1 Hydrogenation reactions
5.2 Oxidative dearomatization reactions
5.3 Dearomatization reactions with nucleophiles
5.4 Dearomatization reactions with electrophiles
5.5 Dearomatization reactions with radicals
5.6 Dearomatization reactions based on η2 or η6 complex
6 Anilines
6.1 Catalytic hydrogenation reactions
6.2 Oxidative dearomatization reactions
6.3 Dearomatization reactions with nucleophiles
6.4 Dearomatization reactions with radicals
6.5 Dearomatization reactions based on η2 complex
7 Pyridines and (iso)quinolines
7.1 Hydrogenation reactions
7.2 Dearomatization reactions with nucleophiles
7.3 Dearomatization reactions with electrophiles
7.4 Dearomatization reactions with dipoles
7.5 Dearomatization reactions with radicals
8 Benzenes and naphthalenes
8.1 Hydrogenation reactions
8.2 Oxidative dearomatization reactions
8.3 Dearomatization reactions with nucleophiles
8.4 Dearomatization reactions with electrophiles
8.5 Dearomatization reactions with radicals
8.6 Cycloaddition dearomatization reactions
8.7 Dearomatization reactions with carbenes
8.8 Rearrangement dearomatization reactions
9 Other arenes
10 Conclusion and outlook
Min Cheng, Lijuan Zhang, Xiling Xu, Hong Gao, Weijun Zheng. The Photodissociation and Photoionization Dynamics of Some Important Small Molecules[J]. Progress in Chemistry, 2024, 36(12): 1830-1848.
The study of microscopic mechanisms of photodissociation and photoionization on small molecules is the major focus in the field of molecular reaction dynamics, which is important from both theoretical and practical aspects. It not only can reveal the physicochemical nature of the interaction between molecules and light, but also can help to understand and eventually regulate the chemical reaction process at the quantum level. This paper systematically reviews the research accomplishments achieved by Academician Zhu Qihe’s group in this field over the years. By utilizing the home-made photofragment translational spectrometers, they have comprehensively explored the photodissociation processes and revealed the microscopic reaction mechanisms for a series of halogenated hydrocarbons in the A band, by measuring the translational energies and spatial angular distributions of the photofragments. They have also investigated the geometric configurations, vibrational spectra, transition energies and ionization energies of benzene derivatives in different electronic states, by using the home-made resonance-enhanced multi-photon ionization and mass-analyzed threshold ionization spectrometers combined with quantum chemical calculations. They summarized the influences of multi-halogen effects, substituent effects and conformational isomerism effects on molecular properties and spectroscopy, supplying important information on the characteristics of excited and ionic states of molecules. These achievements not only deepen our understanding of the microscopic mechanism of chemical reactions, but also provide an important theoretical basis for their practical applications in the fields of atmospheric chemistry, environmental chemistry, biochemistry and material sciences.
Xiaofei Zhang, Chunhao Yang. Recent Development of Small Molecule Drugs for the Treatment of Osteoarthritis[J]. Progress in Chemistry, 2024, 36(12): 1849-1858.
Osteoarthritis is a common degenerative disease in middle-aged and elderly people, and its lesions involve the entire joint, such as cartilage, subchondral bone and synovial membrane. Although there are some launched drugs that can be used to relieve the pain caused by osteoarthritis, the therapeutic effects are insufficient and there are some certain side effects. For now, except for artificial joint replacement for late stage of osteoarthritis, there are no effective drugs for early and middle stage of osteoarthritis to delay its progression. The treatment of osteoarthritis in clinical faces a huge demand for valid drugs, but the development of therapeutic drugs is way behind schedule. This review focuses on the progress of small molecule drugs for the treatment of osteoarthritis, especially the small molecule chemical entities which have entered the clinical trial stage. We hope this article will provide inspiration for the researchers on the drug development of osteoarthritis.
1 Introduction of osteoarthritis
2 Features of osteoarthritis
3 Small molecule drugs against osteoarthritis
3.1 Clinical small molecule drugs against osteoarthritis
3.2 The development of small molecule disease- modifying osteoarthritis drugs (DMOADs)
4 Conclusion and outlook
Xiaoxin Zhang. Green Chemical Technology for the Synthesis of Basic Organic Chemicals[J]. Progress in Chemistry, 2024, 36(12): 1859-1873.
The rapid development of the chemical industry has contributed to global economic growth and improved people's quality of life. However, the massive consumption of fossil fuels in the chemical production process has also caused environmental pollution and climate change that cannot be ignored. Academician Min Enze has been committed to directional fundamental research in green chemistry since 1990. He has introduced and integrated new materials, processes, and reaction pathways into the traditional petrochemical industry, led and guided the implementation of multiple major national basic research projects, accumulated new technological knowledge in green chemistry, laid the foundation for green refining and petrochemical new processes, and developed multiple influential green chemical technologies, effectively promoting the development of green technologies in the petrochemical industry. This article summarizes the green chemical technology practice cases formed on the basis of the catalytic new materials and green chemistry new knowledge laid by Academician Min Enze in the past 20 years, including the green production technology of caprolactam, fluidized bed hydrogen peroxide technology, complete technology of epoxy propane production by hydrogen peroxide method, and green synthesis technology of cyclohexene esterification and hydrogenation. These condensed innovative practices and experiences in catalytic materials and chemical engineering will provide a foundation and reference for us to carry out new technological innovations.
Jian Yang, Yu Liu, Jingyan Li, Pu Chen, Yupeng Xu, Dan Liu, Xiaoli Chu. Research Progress and Prospects of Modern Spectral Fusion Analysis Technology[J]. Progress in Chemistry, 2024, 36(12): 1874-1892.
Multispectral fusion is an important research and development direction in modern spectral analysis techniques. It realizes the information complementarity and synergy of multispectral data by optimizing and integrating different types of spectra. Combined with chemometric methods, it can improve the prediction accuracy and robustness of the models. This paper systematically introduces multispectral fusion strategies and algorithms, including classic fusion strategies, fusion based on multi-block algorithms, fusion based on multi-way algorithms, and fusion based on deep learning. The application research on single-spectral fusion, two-spectral fusion, three-spectral fusion, and the fusion of spectra with other information is respectively summarized and discussed. On this basis, the advantages and disadvantages, limitations, and basic selection principles of spectral fusion methods are reviewed. Finally, the challenges faced by multispectral fusion analysis techniques and the future prospects are discussed.
Jinlan Zhang, Fengguo Xu. Development History and Trends of Pharmaceutical Analysis in China[J]. Progress in Chemistry, 2024, 36(12): 1893-1900.
It is significant to commemorate the 100th anniversary of the birth of Academician Zhou Tonghui, the analytical chemist, and to learn the spirit of great scientists. Academician Zhou led researchers to overcome the difficulties of doping detection and established China’s Doping Control Center, demonstrating his dedication and patriotism. He also made outstanding contributions to the construction and development of the discipline of pharmaceutical analysis. This article is written as a tribute to Mr. Zhou’s contributions and spirit. It introduces the development history of China’s pharmaceutical analysis discipline, the establishment of its educational system, important achievements, and development trends. The article outlines the journey of the discipline from the early days of China, when the older generation of scientists worked hard to improve our pharmaceutical analysis standards, to the rapid development and international prominence achieved since the reform and opening-up period and after. The introduction covers the development of analytical methods and techniques, instruments and apparatus, improvements in drug testing methods, standards and guidance, talent cultivation, key achievements, and future trends.
Junhua Fang, Ruofan Li, Wenjun Zhang, Weixian Zhang. Reductive Transformation of Perchlorate: Fundamentals and Applications[J]. Progress in Chemistry, 2024, 36(12): 1901-1914.
Perchlorate, a persistent inorganic pollutant in water, poses a global environmental challenge due to its high solubility, mobility, and stability, making it difficult to degrade in the environment. Contamination by perchlorate has become a worldwide environmental issue, as residues of perchlorate in surface water and groundwater enter food and drinking water through various pathways, posing potential health risks. Chemical and biological methods have been extensively studied for perchlorate removal, each with its unique advantages and challenges. This paper systematically summarizes the recent research progress in chemical and biological treatment technologies for removing perchlorate from water, elaborating on the mechanisms, influencing factors, and advantages and disadvantages of these technologies. Chemical degradation, catalytic reduction, and electrochemical reduction are effective methods for treating perchlorate pollution. Organic electron donors such as acetate, glycerol, ethanol, and methane, as well as inorganic electron donors such as hydrogen and elemental sulfur, are widely used in the biological degradation process of perchlorate. Chemical methods provide rapid reduction rates and convenient implementation, while biological methods offer environmentally friendly solutions and long-term sustainable potential. However, both methods have limitations. In recent years, researchers have begun to explore combined removal techniques that integrate chemical and biological methods to enhance the remediation efficiency of perchlorate pollution. This paper reviews the research progress of three combined removal techniques: adsorption-biological method, bio-electrochemical method, and chemical reduction-biological method. In addition, future research directions are discussed, including engineering implementation studies, materials and microbiology research, practical application studies, and in-depth exploration of perchlorate degradation mechanisms.
1 Introduction
2 Chemical degradation of perchlorate
2.1 Chemical reduction
2.2 Catalytic reduction
2.3 Electrochemical reduction
3 Biodegradation of perchlorate
3.1 Organic electron donor
3.2 Inorganic electron donor
4 Combined methods for perchlorate degradation
4.1 Adsorption-biological method
4.2 Bio-electrochemical method
4.3 Chemical reduction-biological method
5 Conclusion and Outlook
Sai Zheng, Xiaoyu Guan, Bingyuan Zhang, Yanxia Zhu, Dongping Li, Qingxin Han, Xuechuan Wang. Biomass-Based Ionic Thermoelectric Devices[J]. Progress in Chemistry, 2024, 36(12): 1915-1928.
The new ionic thermoelectric material based on biomass has the advantages of high ionic Seebeck coefficient, good flexibility, low cost, green biodegradability, etc., and has broad application prospects in the construction of safe, stable, and efficient flexible wearable thermoelectric devices. In this paper, the preparation methods, thermoelectric principles, and thermoelectric properties of ionic thermoelectric capacitors and ionic thermocells based on biomass materials such as cellulose and gelatin and their latest applications in wearable body heat collection devices, flexible temperature sensors, and self-driven human monitoring systems in the past five years are reviewed. Combined with the current research, we further summarize the difficulties and shortcomings in the research of biomass-based ionic thermoelectric materials, as well as the difficulties and challenges facing the future promotion and application of biomass-based thermoelectric devices. Finally, we propose targeted solution ideas for the existing problems, providing important theoretical guidance and technical references for related research in this field.
1 Introduction
2 Ionic thermoelectric overview
2.1 Thermoelectric materials
2.2 Ionic thermoelectric effect
2.3 Ionic thermoelectric properties examination index
3 Research progress in biomass-based ionic thermoelectric devices
3.1 Biomass materials overview
3.2 Preparation of biomass-based ionic thermoelectric materials
3.3 Design of biomass-based ionic thermoelectric components
3.4 Functional applications of biomass-based ionic thermoelectric devices
4 Conclusion and outlook
Chenyang Li, Li Su, Qinglei Wang, Xuehui Shangguan, Lijun Gao, Faqiang Li. Research on Construction of Three-Dimensional Current Collector for Stabling Lithium Metal Anodes[J]. Progress in Chemistry, 2024, 36(12): 1929-1943.
Lithium metal is considered to be the most promising anode material owing to its extraordinary theoretical specific capacity and the lowest redox potential. However, lithium anodes suffer from many challenges, such as the uncontrolled growth of lithium dendrites, unstable solid electrolyte interface (SEI) layers, and infinite volume expansion of lithium during cycling, which hinder the further commercial application of lithium metal batteries. Numerous important strategies have been proposed to overcome these challenges. Among them, three-dimensional current collectors can not only reduce the local current density and alleviate dendrite growth, but also mitigate the volume change of Li metal during the stripping/plating process. Based on the above problems, this review summarizes the working mechanisms and the latest research progress about the design of the three-dimensional structure and the lithiophilic modification to stabilize the lithium metal anode.
1 Introduction
2 The design of three-dimensional current collector
2.1 Mechanism of action
2.2 Construction methods
2.3 Structural design
3 Lithiophilic modification
3.1 Lithiophilic mechanism
3.2 Surface modification methods
3.3 Metal-based current collectors
3.4 Carbon-based current collectors
4 Conclusion and outlook
Rong Fan, Yajing Li, Xiaona Hu, Ruiqi Zhang, Xi Liu, Dongshun Zhang, Zhuo Yi. Oxidation Carbonylation Reaction of Terminal Alkynes with Carbon Monoxide/Oxygen[J]. Progress in Chemistry, 2024, 36(12): 1944-1955.
Oxidative carbonylation reactions are powerful methodologies for producing carbonyl derivatives, which show advantages such as wide source of raw materials and a diverse range of products. In recent years, with the concept of environmental protection deeply rooted, developing efficient and green oxidative carbonylation reactions with carbon monoxide and oxygen as reactants, attracts much interest in this field. The C(sp)-H bonds of terminal alkynes exhibit excellent reactivity in oxidative carbonylation reactions, which could form a series of unsaturated carbonyl compounds. This review introduces the oxidative carbonylation reactions of terminal alkynes and their applications in total synthesis, including oxidative alkoxycarbonylation, oxidative aminocarbonylation, and oxidative carbonylation-cyclization, with the focus on the reaction mechanism of carbonylation and metal oxidation. Finally, the future development trends of this field are prospected.
1 Introduction
2 Oxidative alkoxycarbonylation
3 Oxidative aminocarbonylation
4 Oxidative carbonylation-cyclization
5 Application of oxidative carbonylation in total synthesis
6 Conclusion and outlook
Guangyu Pan, Xin Hu, Jie Yin, Yihuan Liu, Kai Guo, Ning Zhu. Synthesis and Ring-Opening Metathesis Polymerization of Bio-Based Cyclic Olefins[J]. Progress in Chemistry, 2024, 36(12): 1956-1971.
The transformations of biomass into bio-based polymeric materials have attracted growing interest from chemistry and material engineering. Ring-opening metathesis polymerizations (ROMP) of cyclic olefins have been identified as the powerful toolbox for synthesis of polyolefins containing double bonds in the polymer mainchains. Recently, a series of novel cyclic olefins are designed by using biomass as the feedstock, and high-performance polyolefins are prepared via ROMP of biomass derived monomers. This review summaries the advances in conversions of cellulose, hemicellulose, lignin, terpenes, vegetable oils, amino acids into norbornene derivatives, oxanorbornene derivatives, cyclooctene derivatives, macrocyclic olefins, etc. Synthesis and properties of bio-based polyolefins via ROMP of biomass derived monomers mentioned above are highlighted. Moreover, the challenges and opportunities are discussed with the aim to promote the development of bio-based polymeric materials.
1 Introduction
2 Cellulose-based cyclic olefins and ROMP
3 Hemicellulose-based cyclic olefins and ROMP
4 Lignin-based cyclic olefins and ROMP
5 Terpenes-based cyclic olefins and ROMP
6 Vegetable oils-based cyclic olefins and ROMP
7 Amino acids-based cyclic olefins and ROMP
8 Conclusion and outlook
Huijing Wang, Die Sun, Ruiying Wang, Hui Zhang. Precision Detection of Tumor Small Extracellular Vesicles[J]. Progress in Chemistry, 2024, 36(12): 1972-1982.
Tumor small extracellular vesicles (sEVs) are membranous vesicles, released by tumor cells, with a particle size less than 200 nm. They carry diverse biomolecular information on their surface and inside, participating in intercellular communication and are recognized as one of the most crucial liquid biopsies for cancer. Because sEVs’ surface contains a variety of proteins that can bind to corresponding antibodies or nucleic acid aptamers, quantitative detection of sEVs can be achieved through optical or electrochemical methods. However, due to the high heterogeneity and complexity of sEVs, relying on a single protein for recognition may lead to false positive or false negative signals. Therefore, accurate detection of tumor-derived sEVs requires simultaneous analysis of multiple biomarkers. Simultaneous analysis of multiple biomarkers can effectively address interference caused by phenotypic heterogeneity in sEVs and provide more accurate guidance for cancer diagnosis and prognosis. This paper focuses on the detection methods of sEVs based on surface proteins using fluorescence, colorimetry, electrochemical methods, and electrochemiluminescence techniques. It emphasizes the importance of achieving high sensitivity and accuracy in detecting sEVs through multi-protein multi-signal proportional output approaches, employing multi-protein logic gates and multi-protein proximity linking reactions.
1 Introduction
2 General analysis method of small extracellular vesicles
2.1 Fluorometry
2.2 Colorimetry
2.3 Electrochemical method
2.4 Electrochemical luminescence
3 Precision detection of small extracellular vesicles based on surface multiproteins
3.1 Multiprotein proportional output
3.2 Multiprotein Logical Computation Output
3.3 Multiprotein proximity ligation reaction
4 Conclusion and outlook