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Recent Advances in Transition Metal Catalysis

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Chemistry".

Deadline for manuscript submissions: closed (31 October 2024) | Viewed by 16140

Special Issue Editor


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Guest Editor
College of Sciences, Northeastern University, Shenyang 110004, China
Interests: photocatalysis; electrosynthesis; transition metal catalysis; polymer chemistry; C–H activation
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Special Issue Information

Dear Colleagues,

Transition metal catalysis is one of the essential tools in modern organic synthesis chemistry and can be applied to various organic synthetic reactions, including C-H/C-C/C-X functionalization, cyclization, and de-aromatization, among others. While noble metals such as ruthenium, rhodium, iridium, and palladium have been extensively studied in catalysis, reactions catalyzed using inexpensive 3D metals such as manganese, iron, cobalt, and nickel have gradually become a current research hotspot. In addition, the use of visible light/electrochemistry and transition metal co-catalysis strategies to achieve the synthesis of structurally diverse and functionally rich organic small molecules has received widespread attention. The use of transition metal catalysis technology in organic synthesis increases the efficiency of chemical reactions, makes synthetic pathways more concise, and lowers production costs. Thus, their deployment not only greatly promotes the development of chemical science but also brings enormous positive impacts to fields such as medicine, pesticides, advanced materials, national defense, and military industry, etc.

This Special Issue aims to provide a broad survey of the most recent advances in transition metal-catalyzed synthesis. The guest editor welcomes reviews and original research articles associated with recent achievements related to the formation of C-C/C-X bonds along transition metal-catalyzed pathways.

Prof. Dr. Dingyi Wang
Guest Editor

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Keywords

  • transition metal catalysis
  • photocatalysis
  • electrosynthesis
  • organic synthesis
  • asymmetric synthesis
  • C-H functionalization
  • C-C functionalization
  • C-X functionalization

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Related Special Issue

Published Papers (10 papers)

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Research

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16 pages, 3205 KiB  
Article
Nickel-Catalyzed Three-Component 1,2-Carboacylation of Alkenes
by Shengzhou Jin, Lanfen Wang, Yinggang Jia, Wenbo Ma and Dingyi Wang
Molecules 2024, 29(18), 4295; https://doi.org/10.3390/molecules29184295 - 10 Sep 2024
Viewed by 699
Abstract
Ketones, prevalent in many biologically significant molecules, require the development of novel methods to synthesize these structures, which is a critical endeavor in organic synthesis. Transition metal catalysis has proven to be an effective method for synthesizing ketones. However, the scope of these [...] Read more.
Ketones, prevalent in many biologically significant molecules, require the development of novel methods to synthesize these structures, which is a critical endeavor in organic synthesis. Transition metal catalysis has proven to be an effective method for synthesizing ketones. However, the scope of these substrates remains relatively limited, particularly due to their incompatibility with sensitive functional groups. Herein, we report a Ni-catalyzed three-component 1,2-carboacylation of alkenes, which activates secondary/tertiary alkyl bromides. This method offers significant advantages: simplicity of operation, ready availability of substrates, and broad substrate applicability. A series of experimental studies have helped clarify the key mechanistic pathways involved in this cascade reaction. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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14 pages, 3919 KiB  
Article
α-Carbonyl Rh-Carbenoid Initiated Cascade Assembly of Diazobarbiturates with Alkylidene Pyrazolones for Synthesis of Spirofuropyrimidines
by Yue Zhang, Yu-Hang Mi, Kuo Wang and Hong-Wu Zhao
Molecules 2024, 29(13), 3178; https://doi.org/10.3390/molecules29133178 - 3 Jul 2024
Viewed by 960
Abstract
Catalyzed by Rh2(esp)2 (10 mol%) and (±)-BINAP (20 mol%) in DCE at 80 °C, the cascade assembly between diazobarbiturates and alkylidene pyrazolones proceeded readily and produced spiro-furopyrimidines in 38–96% chemical yields. The chemical structure of the prepared spirofuro-pyrimidines was firmly [...] Read more.
Catalyzed by Rh2(esp)2 (10 mol%) and (±)-BINAP (20 mol%) in DCE at 80 °C, the cascade assembly between diazobarbiturates and alkylidene pyrazolones proceeded readily and produced spiro-furopyrimidines in 38–96% chemical yields. The chemical structure of the prepared spirofuro-pyrimidines was firmly confirmed by X-ray diffraction analysis. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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12 pages, 1824 KiB  
Article
Intensive Treatment of Organic Wastewater by Three-Dimensional Electrode System within Mn-Loaded Steel Slag as Catalytic Particle Electrodes
by Xu Ren, Haifeng Fu, Danni Peng, Meng Shen, Peixin Tang, Kai Song, Bo Lai and Zhicheng Pan
Molecules 2024, 29(5), 952; https://doi.org/10.3390/molecules29050952 - 21 Feb 2024
Viewed by 1110
Abstract
Developing a green, low-carbon, and circular economic system is the key to achieving carbon neutrality. This study investigated the organics removal efficiency in a three-dimensional electrode reactor (3DER) constructed from repurposed industrial solid waste, i.e., Mn-loaded steel slag, as the catalytic particle electrodes [...] Read more.
Developing a green, low-carbon, and circular economic system is the key to achieving carbon neutrality. This study investigated the organics removal efficiency in a three-dimensional electrode reactor (3DER) constructed from repurposed industrial solid waste, i.e., Mn-loaded steel slag, as the catalytic particle electrodes (CPE). The CPE, a micron-grade material consisting primarily of transition metals, including Fe and Mn, exhibited excellent electric conductivity, catalytic ability, and recyclability. High rhodamine B (RhB) removal efficiency in the 3DER was observed through a physical modelling experiment. The optimal operating condition was determined through a single-factor experiment in which 5.0 g·L−1 CPE and 3 mM peroxymonosulfate (PMS) were added to a 200 mL solution of 10 mM RhB under a current intensity of 0.5 A and a 1.5 to 2.0 cm distance between the 2D electrodes. When the initial pH value of the simulated solution was 3 to 9, the RhB removal rate exceeded 96% after 20 min reaction. In addition, the main reactive oxidation species in the 3DER were determined. The results illustrated that HO• and SO4•− both existed, but that the contribution of SO4•− to RhB removal was much lower than that of HO• in the 3DER. In summary, this research provides information on the potential of the 3DER for removing refractory organics from water. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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10 pages, 1692 KiB  
Communication
Oxygen-Free Csp3-H Oxidation of Pyridin-2-yl-methanes to Pyridin-2-yl-methanones with Water by Copper Catalysis
by Ming Zeng, Jia-Le Chen, Xue Luo, Yan-Jiao Zou, Zhao-Ning Liu, Jun Dai, Deng-Zhao Jiang and Jin-Jing Li
Molecules 2023, 28(22), 7587; https://doi.org/10.3390/molecules28227587 - 14 Nov 2023
Viewed by 1130
Abstract
Aromatic ketones are important pharmaceutical intermediates, especially the pyridin-2-yl-methanone motifs. Thus, synthetic methods for these compounds have gained extensive attention in the last few years. Transition metals catalyze the oxidation of Csp3-H for the synthesis of aromatic ketones, which is arresting. [...] Read more.
Aromatic ketones are important pharmaceutical intermediates, especially the pyridin-2-yl-methanone motifs. Thus, synthetic methods for these compounds have gained extensive attention in the last few years. Transition metals catalyze the oxidation of Csp3-H for the synthesis of aromatic ketones, which is arresting. Here, we describe an efficient copper-catalyzed synthesis of pyridin-2-yl-methanones from pyridin-2-yl-methanes through a direct Csp3-H oxidation approach with water under mild conditions. Pyridin-2-yl-methanes with aromatic rings, such as substituted benzene, thiophene, thiazole, pyridine, and triazine, undergo the reaction well to obtain the corresponding products in moderate to good yields. Several controlled experiments are operated for the mechanism exploration, indicating that water participates in the oxidation process, and it is the single oxygen source in this transformation. The current work provides new insights for water-involving oxidation reactions. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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17 pages, 3169 KiB  
Article
Machine Learning and Quantum Calculation for Predicting Yield in Cu-Catalyzed P–H Reactions
by Youfu Ma, Xianwei Zhang, Lin Zhu, Xiaowei Feng, Jamal A. H. Kowah, Jun Jiang, Lisheng Wang, Lihe Jiang and Xu Liu
Molecules 2023, 28(16), 5995; https://doi.org/10.3390/molecules28165995 - 10 Aug 2023
Viewed by 2022
Abstract
The paper discussed the use of machine learning (ML) and quantum chemistry calculations to predict the transition state and yield of copper-catalyzed P–H insertion reactions. By analyzing a dataset of 120 experimental data points, the transition state was determined using density functional theory [...] Read more.
The paper discussed the use of machine learning (ML) and quantum chemistry calculations to predict the transition state and yield of copper-catalyzed P–H insertion reactions. By analyzing a dataset of 120 experimental data points, the transition state was determined using density functional theory (DFT). ML algorithms were then applied to analyze 16 descriptors derived from the quantum chemical transition state to predict the product yield. Among the algorithms studied, the Support Vector Machine (SVM) achieved the highest prediction accuracy of 97%, with over 80% correlation in Leave-One-Out Cross-Validation (LOOCV). Sensitivity analysis was performed on each descriptor, and a comprehensive investigation of the reaction mechanism was conducted to better understand the transition state characteristics. Finally, the ML model was used to predict reaction plans for experimental design, demonstrating strong predictive performance in subsequent experimental validation. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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Review

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28 pages, 7253 KiB  
Review
Transition-Metal-Catalyzed Directed C–H Bond Functionalization with Iodonium Ylides: A Review of the Last 5 Years
by Juting Liao, Dulin Kong, Xiaoyang Gao, Ruirui Zhai, Xun Chen and Shuojin Wang
Molecules 2024, 29(15), 3567; https://doi.org/10.3390/molecules29153567 - 29 Jul 2024
Viewed by 955
Abstract
Transition-metal-catalyzed directed C–H functionalization with various carbene precursors has been widely employed for constructing a wide range of complex and diverse active molecules through metal carbene migratory insertion processes. Among various carbene precursors, iodonium ylides serve as a novel and emerging carbene precursor [...] Read more.
Transition-metal-catalyzed directed C–H functionalization with various carbene precursors has been widely employed for constructing a wide range of complex and diverse active molecules through metal carbene migratory insertion processes. Among various carbene precursors, iodonium ylides serve as a novel and emerging carbene precursor with features including easy accessibility, thermal stability and high activity, which have attracted great attention from organic chemists and have achieved tremendous success in organic transformation. In this review, recent progress on the application of iodonium ylides with multifunctional coupling characteristics in C–H bond activation reactions is summarized, and the potential of iodonium ylides is discussed. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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16 pages, 4061 KiB  
Review
Recent Advances in the Research on Luotonins A, B, and E
by Ján Gettler, Martin Markovič, Peter Koóš and Tibor Gracza
Molecules 2024, 29(15), 3522; https://doi.org/10.3390/molecules29153522 - 26 Jul 2024
Viewed by 470
Abstract
This digest review summarises the most recent progress in the study on luotonins A, B and E. The literature covered in this overview spans from January 2012 to April 2024 and presents synthetic methodologies for the assembly of the quinolinopyrrolo-quinazoline scaffold, the structural [...] Read more.
This digest review summarises the most recent progress in the study on luotonins A, B and E. The literature covered in this overview spans from January 2012 to April 2024 and presents synthetic methodologies for the assembly of the quinolinopyrrolo-quinazoline scaffold, the structural motifs present in luotonins A, B, and E, and the evaluation of the biological activities of their derivatives and structural analogues. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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28 pages, 5149 KiB  
Review
Heterogeneous Iron-Based Catalysts for Organic Transformation Reactions: A Brief Overview
by Manash J. Baruah, Rupjyoti Dutta, Magdi E. A. Zaki and Kusum K. Bania
Molecules 2024, 29(13), 3177; https://doi.org/10.3390/molecules29133177 - 3 Jul 2024
Cited by 3 | Viewed by 1587
Abstract
Iron (Fe) is considered to be one of the most significant elements due to its wide applications. Recent years have witnessed a burgeoning interest in Fe catalysis as a sustainable and cost-effective alternative to noble metal catalysis in organic synthesis. The abundance and [...] Read more.
Iron (Fe) is considered to be one of the most significant elements due to its wide applications. Recent years have witnessed a burgeoning interest in Fe catalysis as a sustainable and cost-effective alternative to noble metal catalysis in organic synthesis. The abundance and low toxicity of Fe, coupled with its competitive reactivity and selectivity, underscore its appeal for sustainable synthesis. A lot of catalytic reactions have been performed using heterogeneous catalysts of Fe oxide hybridized with support systems like aluminosilicates, clays, carbonized materials, metal oxides or polymeric matrices. This review provides a comprehensive overview of the latest advancements in Fe-catalyzed organic transformation reactions. Highlighted areas include cross-coupling reactions, C–H activation, asymmetric catalysis, and cascade processes, showcasing the versatility of Fe across a spectrum of synthetic methodologies. Emphasis is placed on mechanistic insights, elucidating the underlying principles governing iron-catalyzed reactions. Challenges and opportunities in the field are discussed, providing a roadmap for future research endeavors. Overall, this review illuminates the transformative potential of Fe catalysis in driving innovation and sustainability in organic chemistry, with implications for drug discovery, materials science, and beyond. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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18 pages, 4440 KiB  
Review
Recent Progress in Photocatalytic Degradation of Water Pollution by Bismuth Tungstate
by Yingjie Zhang, Huijuan Yu, Ruiqi Zhai, Jing Zhang, Cuiping Gao, Kezhen Qi, Li Yang and Qiang Ma
Molecules 2023, 28(24), 8011; https://doi.org/10.3390/molecules28248011 - 8 Dec 2023
Cited by 10 | Viewed by 3342
Abstract
Photocatalysis has emerged as a highly promising, green, and efficient technology for degrading pollutants in wastewater. Among the various photocatalysts, Bismuth tungstate (Bi2WO6) has gained significant attention in the research community due to its potential in environmental remediation and [...] Read more.
Photocatalysis has emerged as a highly promising, green, and efficient technology for degrading pollutants in wastewater. Among the various photocatalysts, Bismuth tungstate (Bi2WO6) has gained significant attention in the research community due to its potential in environmental remediation and photocatalytic energy conversion. However, the limited light absorption ability and rapid recombination of photogenerated carriers hinder the further improvement of Bi2WO6’s photocatalytic performance. This review aims to present recent advancements in the development of Bi2WO6-based photocatalysts. It delves into the photocatalytic mechanism of Bi2WO6 and summarizes the achieved photocatalytic characteristics by controlling its morphology, employing metal and non-metal doping, constructing semiconductor heterojunctions, and implementing defective engineering. Additionally, this review explores the practical applications of these modified Bi2WO6 photocatalysts in wastewater purification. Furthermore, this review addresses existing challenges and suggests prospects for the development of efficient Bi2WO6 photocatalysts. It is hoped that this comprehensive review will serve as a valuable reference and guide for researchers seeking to advance the field of Bi2WO6 photocatalysis. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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24 pages, 4944 KiB  
Review
Transition Metal Catalysts for Atmospheric Heavy Metal Removal: A Review of Current Innovations and Advances
by Qiang Ma, Xianglong Zhang, Jie Li, Yingjie Zhang, Qingyuan Wang, Li Zeng, Yige Yang, Yonghong Xie and Jin Huang
Molecules 2023, 28(22), 7620; https://doi.org/10.3390/molecules28227620 - 16 Nov 2023
Cited by 3 | Viewed by 2899
Abstract
Atmospheric heavy metal pollution presents a severe threat to public health and environmental stability. Transition metal catalysts have emerged as a potent solution for the selective capture and removal of these pollutants. This review provides a comprehensive summary of current advancements in the [...] Read more.
Atmospheric heavy metal pollution presents a severe threat to public health and environmental stability. Transition metal catalysts have emerged as a potent solution for the selective capture and removal of these pollutants. This review provides a comprehensive summary of current advancements in the field, emphasizing the efficiency and specificity of nanostructured transition metals, including manganese, iron, cobalt, nickel, copper, and zinc. Looking forward, we delve into the prospective trajectory of catalyst development, underscoring the need for materials with enhanced stability, regenerability, and environmental compatibility. We project that advancements in computational materials science, nanotechnology, and green chemistry will be pivotal in discovering innovative catalysts that are economically and environmentally sustainable. The integration of smart technologies for real-time monitoring and adaptive control is anticipated to revolutionize heavy metal remediation, ensuring efficient and responsive pollution abatement strategies in the face of evolving industrial scenarios and regulatory landscapes. Full article
(This article belongs to the Special Issue Recent Advances in Transition Metal Catalysis)
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