Article
Chemistry, Organic
Paul Shaw, Storm J. Hassell-Hart, Gayle E. Douglas, Andrew G. Malcolm, Alan R. Kennedy, Gemma White, Laura C. Paterson, William J. Kerr
Summary: In this study, we applied silyl enol ether moieties as efficient alkene coupling partners within cobalt-mediated intramolecular Pauson-Khand reactions. This cyclization strategy delivers valuable oxygenated cyclopentenone products in high yields and allows for the incorporation of a variety of decorated structures.
Review
Chemistry, Physical
Sourav Biswas, Saikat Das, Yuichi Negishi
Summary: This Minireview provides a comprehensive coverage of the optimal design strategies and controlled synthesis of copper nanoclusters (Cu NCs) as catalysts. It discusses the tuning of active sites at the atomic level, the influence of cluster size, shape, structure, ligands and heteroatom doping on catalytic activity, and various catalytic applications ranging from chemical catalysis to emerging photocatalysis and electrocatalysis.
NANOSCALE HORIZONS
(2023)
Article
Chemistry, Multidisciplinary
Sanghwa Lee, Megalamane S. Bootharaju, Guocheng Deng, Sami Malola, Hannu Hakkinen, Nanfeng Zheng, Taeghwan Hyeon
Summary: Heteroatom-doped metal nanoclusters are synthesized by a metal-exchange strategy, leading to the discovery that Pt doping can significantly enhance the catalytic activity of Cu nanoclusters by around 300-fold. This synthetic approach has the potential to produce Ni-, Pd-, and Au-doped Cu nanoclusters, opening new avenues for studying their molecular structures and catalytic properties.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Xu Li, Lu Lanlan, Wang Xiangshan
Summary: A method for the rapid synthesis of beta-keto sulfones catalyzed by copper bromide from enol silyl ether and sodium arylsulfinates has been developed, which offers the advantages of simple operation, mild conditions, and short reaction time.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Applied
Asit Kumar Das, Sneha Nandy, Sanjay Bhar
Summary: An economically efficient and operationally simple ligand-free protocol has been developed for the chemoselective oxidation of benzylic alcohols to carbonyl compounds using alumina-supported nickel nanoparticles. The protocol demonstrates excellent chemoselectivity and tolerance towards various sensitive moieties, with the catalyst being recyclable without significant loss in activity. The heterogeneous nature of the catalyst has been established, making it a promising eco-friendly option for oxidation reactions.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yingwei Li, Hong Ki Kim, Ryan D. McGillicuddy, Shao-Liang Zheng, Kevin J. Anderton, Grant J. Stec, Jaehyeong Lee, Dongtao Cui, Jarad A. Mason
Summary: In this study, Au43(C-CtBu)20 and Au42Ag1(C-CtBu)20 metal nanoclusters with open electronic and geometric shells were reported, showing paramagnetism and enhanced catalytic activity from a single coordinatively unsaturated surface metal. These nanoclusters exhibit helical stripes around the inner Au12 kernel, giving them chirality and high thermal stability. Experimental and theoretical calculations showed minimal energy differences between the open-shelled nanoclusters and hypothetical closed-shell systems, and the open-shelled configuration resulted in the largest band gap, thus promoting cluster stability. Additionally, the coordinatively unsaturated surface metals were found to create active sites for catalytic oxidation, leading to high selectivity and conversion. This study provides a promising platform for investigating the magnetic and catalytic properties of noble metal nanoparticles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Goh Sennari, Kristen E. Gardner, Stefan Wiesler, Maximilian Haider, Alina Eggert, Richmond Sarpong
Summary: Guided by chemical network analysis, the synthetic studies towards C18- and C19-benzenoid cephalotane-type norditerpenoids were carried out, leading to the construction of core structure in a concise manner and improvement of efficiency through reaction optimization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Maximilian Haider, Goh Sennari, Alina Eggert, Richmond Sarpong
Summary: This research presents a concise synthesis method for cephanolides A-D of Cephalotaxus norditerpenoids, utilizing a common late-stage synthetic intermediate and employing chemical network analysis and Csp(2)-Csp(3) cross-coupling for efficient construction of the carbon framework. Strategic late-stage oxidations were crucial in accessing all congeners of the benzenoid cephanolides isolated to date.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Physical
Katsuhiro Isozaki, Ryo Ueno, Kosuke Ishibashi, Genta Nakano, Haozhi Yin, Kenta Iseri, Masanori Sakamoto, Hikaru Takaya, Toshiharu Teranishi, Masaharu Nakamura
Summary: This study describes the synthesis of gold nanoclusters functionalized by peptide dendron thiolate ligands to form a hydrogen bonding supramolecular reaction field. The prepared nanoclusters act as efficient photocatalysts for oxidative cyclization, with dynamic transformation of hydrogen bonds between ligands playing a key role in accelerating the reaction. The concept introduced in this work allows for tuning reactivities and selectivities of metal nanocluster catalysts using supramolecular reaction fields created with dendritic thiolate ligands.
Article
Chemistry, Multidisciplinary
Zhikun Peng, Rongkui Chen, Hongji Li
Summary: Heterogeneous photocatalytic systems have been developed to selectively degrade polystyrene (PS) to aromatic monomers at room temperature and ambient pressure. By modifying TiO2 particles with potassium stearate or N,N-diethyl-3-(trimethoxysilyl)propan-1-amine, the oxidative cleavage of commercial PS to benzoic acid can achieve up to 43.5 mol % yield. The use of alkaline modifiers greatly improves the C-H oxidation and C-C cleavage reactions, and the key oxidative species in the degradation process are found to be the superoxide anion radical and single oxygen. Furthermore, this study demonstrates the efficient degradation of common PS waste to benzoic acid on the developed photocatalysts with yields ranging from 18 to 44.2 mol %.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Wenjie Zhang, Huimin Kong, Zhennan Wu, Qaofeng Yao, Linan Wang, Liang Quo, Yanjie He, Xiaoguang Qiao, Xinchang Pang, Jianping Xie
Summary: The controlled synthesis of ultrasmall metal nanocluster (NC) assemblies with a specific size and number of NCs can be achieved using star-like diblock copolymer unimolecular micelles as a scaffold. The length of the P4VP block in the polymers can be adjusted to control the size of the NC assemblies. Thiolate ligands play a crucial role in determining the size of individual nanoclusters and enhancing the stability of the NC assemblies, which have promising applications in catalysis, optics, and biomedicine.
CHEMISTRY OF MATERIALS
(2021)
Article
Chemistry, Physical
Shan Gao, Linxia Wang, Hui Li, Zunfeng Liu, Guoliang Shi, Jianfei Peng, Bin Wang, Weichao Wang, Kyeongjae Cho
Summary: Reducing sulfur poisoning through alloying and core-shell structure design of nanoclusters can optimize catalytic behaviors.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Inorganic & Nuclear
Qun Chen, Cheng-Yang Jiao, Hu Xu, Si-Man Li, Jian-Bo Yang, Hua Mei, Yan Xu
Summary: In this study, a copper-modified isolated dimeric hybrid nanocluster was synthesized for efficient and clean photocatalytic one-step oxidation to phenol. The modified cluster not only solves some problems in the traditional phenol production process but also introduces copper atoms as a second active center, improving the catalytic performance.
DALTON TRANSACTIONS
(2023)
Article
Materials Science, Multidisciplinary
Tianyou Chen, Zihao Wang, Wei Xiao, Changfeng Yi, Zushun Xu
Summary: A controllable and efficient strategy was devised for the preparation of supported multifunctional catalysts, which showed high efficiency for the aerobic oxidation of benzyl alcohol. Cooperative behaviors could be regulated by precise control of local concentrations of functional groups, leading to enhanced catalytic performance.
ACS APPLIED POLYMER MATERIALS
(2021)
Article
Polymer Science
Benben Zhang, Zeyu Ye, Min Qin, Qingqing Wang, Yijun Du, Chenze Qi, Linjun Shao
Summary: A simple and green chemical modification method combined with electrospinning technique was used to incorporate palladium active species into crosslinked polystyrene nanofibers, resulting in an efficient and stable heterogeneous palladium catalyst (Pd@CPS). The Pd@CPS catalyst exhibited high catalytic activities and recyclabilities for Suzuki and Heck reactions of aromatic iodides, with coupling yields exceeding 88%. The ultrafine fiber structure and embedment of palladium active species inside the nanofibers contributed to the high activities and stabilities of the prepared Pd@CPS catalyst.
JOURNAL OF APPLIED POLYMER SCIENCE
(2021)
Article
Chemistry, Organic
Tomohiro Yasukawa, Xi Yang, Shu Kobayashi
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Tomohiro Yasukawa, Zhiyuan Zhu, Yasuhiro Yamashita, Shu Kobayashi
Summary: A ligand-free approach using polysilane/alumina-supported palladium nanoparticles has been developed for carbonylative Suzuki-Miyaura coupling reactions to synthesize diaryl ketones. This method shows high yields and selectivities even with low catalyst loading under atmospheric pressure of CO gas. The immobilized palladium nanoparticles can be easily recovered by filtration and maintain catalytic activity for several runs.
Article
Chemistry, Multidisciplinary
Xi Yang, Tomohiro Yasukawa, Tei Maki, Yasuhiro Yamashita, Shu Kobayashi
Summary: In this study, heterogeneous trifluoromethanesulfonic acid immobilized nitrogen-doped carbon-incarcerated titanium nanoparticle (NP) catalysts were developed, showing high activity for Friedel-Crafts acylation with low titanium loading. The addition of metals further changed the nature of the acidic species and enhanced catalytic activity, providing a promising approach for organic transformations.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Ryusuke Masuda, Tomohiro Yasukawa, Yasuhiro Yamashita, Shu Kobayashi
Summary: The development of a stable heterogeneous catalyst system using Rh nanoparticle catalysts supported on nitrogen-doped carbon has allowed for successful asymmetric catalysis reactions, achieving high yields and enantioselectivities of chiral alpha-amino acid derivatives. Nitrogen dopants played a crucial role in both catalytic activity and enantioselectivity, with the catalyst showing reusability in seven runs and efficiency in a continuous-flow reaction for over 90 hours.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Applied
Tatsuya Kuremoto, Ren Sadatsune, Tomohiro Yasukawa, Yasuhiro Yamashita, Shu Kobayashi
Summary: In this study, a ligand library containing 31 chiral diamines was synthesized and evaluated in a continuous-flow asymmetric 1,4-addition reaction. A prediction model for enantioselectivities was successfully constructed based on experimental results and virtual screening was conducted to identify promising structures with good enantioselectivities in experiments.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Editorial Material
Chemistry, Multidisciplinary
Tomohiro Yasukawa, Shu Kobayashi
ACS CENTRAL SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Tomohiro Yasukawa, Sanshiro Kume, Yasuhiro Yamashita, Shu Kobayashi
Summary: Nitrogen-doped carbon-supported Co/Cu bimetallic catalysts were found to efficiently catalyze the olefination of various aromatic aldehydes into unsaturated esters in the presence of triaryl phosphine, allowing for the recovery and reuse of the catalyst without significant loss of activity over multiple runs.
Article
Chemistry, Organic
Xi Yang, Tomohiro Yasukawa, Yasuhiro Yamashita, Shu Kobayashi
Summary: Heterogeneous catalysts immobilized with trifluoromethanesulfonic acid on nitrogen-doped carbon-incarcerated niobia nanoparticles (NCI-Nb-TfOH) have been developed, showing excellent catalytic performance with low niobium loading (1 mol %) in Friedel-Crafts acylation. These catalysts exhibit higher activity and tolerance to catalytic poisons compared to previously reported TfOH-treated NCI-Ti catalysts, leading to a broader substrate scope.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Ryusuke Masuda, Tomohiro Yasukawa, Yasuhiro Yamashita, Shu Kobayashi
Summary: Electrochemical allylation reactions of carbonyl compounds using cathodes prepared from nitrogen-doped carbon-incarcerated zinc catalysts have been developed. The desired allylic alcohols were obtained in high yields with low zinc leaching, suggesting the heterogeneous nature of the catalyst. Compared to bulk zinc electrodes, the nitrogen-doped carbon-stabilized zinc nanoparticle catalysts were compatible with a broader range of substrates, including heteroaromatic compounds, and enabled the use of an undivided cell.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Tatsuya Kuremoto, Ren Sadatsune, Tomohiro Yasukawa, Shu Kobayashi
Summary: A novel core/shell structure support was designed to enhance the accessibility of reaction sites, showing higher catalytic activity in asymmetric 1,4-addition reactions. This design strategy may offer a general approach for obtaining other heterogeneous catalysts with high activities.
Article
Chemistry, Physical
Fumiya Tobita, Tomohiro Yasukawa, Yasuhiro Yamashita, Shu Kobayashi
Summary: The developed catalysts can efficiently oxidize alcohols to aldehydes with high yields. Stable long-term reactions can be achieved by tuning the flow rate. Additionally, the catalysts allow for the continuous synthesis of unsaturated carbonyl compounds without isolating intermediates.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Hiroyuki Miyamura, Shu Kobayashi
Summary: This paper describes the development of cooperative and synergistic catalyst systems of heterogeneous Rh-Pt bimetallic nanoparticle catalysts, Rh-Pt/DMPSi-Al2O3, and Sc(OTf)(3) in the liquid phase for the hydrogenation of arenes under very mild conditions. The cooperative activation achieved significant rate acceleration and successful hydrogenation of challenging substrates with strong electron-donating groups and sterically hindered substituents was demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Tomohiro Yasukawa, Karin Sakamoto, Yasuhiro Yamashita, Shu Kobayashi
Summary: This study developed a catalyst with nitrogen-doped carbon as a carrier to achieve the homologation of aryl aldehydes, which showed excellent performance in terms of selectivity, activity, and reusability.
Article
Chemistry, Organic
Tomohiro Yasukawa, Hanako Nakajima, Ryusuke Masuda, Yasuhiro Yamashita, Shu Kobayashi
Summary: This study comprehensively investigated the heat-drying methods of molecular sieves for imine synthesis. It was found that drying molecular sieve 5A at 160 degrees C for 5 hours under vacuum effectively promoted the condensation reaction of ketones and amines. Only a small amount of Bronsted acid sites were crucial for the activity, rather than dehydration ability. Other types of molecular sieves could also be used after treatment with water and heat drying. Additionally, the application of activated molecular sieve 5A in the continuous-flow acetalization reaction of alcohols was demonstrated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Tomohiro Yasukawa, Xi Yang, Yasuhiro Yamashita, Shu Kobayashi
Summary: A metal-free, heterogeneous acid catalyst has been developed for Povarov reactions. This catalyst shows excellent catalytic activity and selectivity, and has a wide range of substrate applicability. The catalytic system is heterogeneous and reusable, and has been characterized through spectroscopic and microscopic analysis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Fuying Zhu, Yamei Lin
Summary: In this study, a low-metal iron-supported catalyst (Fe20/NC-Mg) was reported for the efficient synthesis of quinoxaline compounds, using water as a solvent and without additional bases. The synergistic effect of FeNx site and Mg (OH)2 nanorods in the catalyst played a key role in achieving high yields (82-91%) in 16 examples. The gram-level synthesis and reusability of the catalysts after four cycles demonstrated its industrial application potential.
Article
Chemistry, Organic
Mikhail Kozlov, Alexey Tyurin, Andrey Dmitrenok, Vyacheslav Rusak, Aleksander Fedorov, Igor Zavarzin, Yulia Volkova
Summary: This study presents a novel and practical synthesis method for phosphorus-substituted 1,3,4-thiadiazolines using phosphorylthioformic acid hydrazides and ketones. The protocol demonstrates operational simplicity, availability of reagents, and tolerance towards different functional groups.
Article
Chemistry, Organic
Jisna Jose, Thomas Mathew
Summary: 2-Cyclopentenone and its derivatives are highly esteemed synthetic intermediates with exceptional utility in organic synthesis. They are favored structural motifs in numerous pharmaceutical drugs and natural products, highlighting their significance. The review discusses the various methods used to synthesize cyclopentenones from 2016 to 2023.
