Article
Chemistry, Multidisciplinary
Sophi R. Todtz, Cory W. Schneider, Tanmay Malakar, Clare Anderson, Heather Koska, Paul M. Zimmerman, James J. Devery
Summary: Lewis acid-catalyzed carbonyl-olefin metathesis has revealed new behaviors of Lewis acids, particularly the solution behaviors of FeCl3. Adding TMSCl to FeCl3-catalyzed carbonyl-olefin metathesis leads to significant deviations from normal reactivity, mitigating byproduct inhibition and increasing the reaction rate. Quantum chemical simulations suggest the formation of a silylium catalyst that binds to carbonyl groups, with potential utility in carbonyl-based transformations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Peter-Yong Wang, Itai Massad, Ilan Marek
Summary: The facile and modular access to stereodefined disubstituted aldehyde-derived silyl enol ethers allowed for their successful application in a stereoselective aldol reaction, resulting in excellent yields and diastereomeric ratios. The counter-intuitive stereochemical behavior of this Mukaiyama-aldol reaction is explained by a non-classical open transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Masahito Yoshida, Yuhi Okoshi, Hideo Kigoshi
Summary: A concise total synthesis of metacridamides A and B was achieved through repetitive vinylogous Mukaiyama aldol reactions and ynamide-mediated macrolactonization. The spectral data of the synthetic products matched those of the natural compounds, leading to the reassessment of the absolute configuration of the C-9 position as S.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Natalie C. Dwulet, Vincenzo Ramella, Christopher D. Vanderwal
Summary: Soft enolization conditions are shown to be more efficient than hard enolization protocols in regioselectively forming enoxysilanes from unsymmetrical 3-substituted cycloalkanones. The regioselectivities achieved are complementary to those obtained from cycloalkenone conjugate addition/enolate silylation with high selectivity.
Article
Chemistry, Organic
Kwihwan Kobayashi, Shingo Komatsuzaki, Shun-ya Onozawa, Koichiro Masuda, Shu Kobayashi
Summary: We present a green method for the synthesis of aryl enol ethers from phenols and dimethyl ketals using aluminium as a catalyst, without halides and transition metals. The ketal exchange reaction is driven by the removal of methanol. The obtained aryl enol ethers can be transformed into diaryl ethers through Pd/C-catalysed dehydrogenation or DDQ oxidation. This method is significant for the synthesis of important intermediates or building blocks in organic synthesis and polymer chemistry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Kwihwan Kobayashi, Shingo Komatsuzaki, Shun-ya Onozawa, Koichiro Masuda, Shu Kobayashi
Summary: We present an aluminium-catalysed, halide- and transition metal-free method for synthesizing aryl enol ethers from phenols and dimethyl ketals through ketal exchange driven by methanol removal. The obtained aryl enol ethers can be further transformed into diaryl ethers using Pd/C-catalysed dehydrogenation or DDQ oxidation. This new protocol provides a halide- and transition metal-free approach for the synthesis of phenols and dimethyl ketals, which are important intermediates or building blocks in organic synthesis and polymer chemistry.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Nikhil Srivastava, Hyun-Joon Ha
Summary: A straightforward and highly diastereoselective synthesis of beta-(aziridin-2-yl)-beta-hydroxy ketones was achieved via the Mukaiyama aldol reaction, with excellent yields and diastereoisomeric ratio. These ketones were further utilized in the synthesis of various alkaloids, demonstrating their versatile applications in organic synthesis.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Masahiro Murakami
Summary: This essay highlights the life and contributions of Professor Teruaki Mukaiyama, emphasizing his insightful mentorship and significant scientific impact on the chemical community. It serves as a lasting tribute to his didactic guidance and encouragement for future generations.
Article
Chemistry, Organic
Xi-Yu Wang, Min Yang, Ying Zhou, Jian Zhou, Yong-Jia Hao
Summary: A highly efficient metal-free selective 1,4-addition reaction of difluoroenoxysilanes to chromones was developed using HOTf as the catalyst, providing a facile method to access valuable C2-difluoroalkylated chroman-4-one derivatives. The products could be converted to the difluorinated bioisostere of the natural product (S)-2,6-dimethylchroman-4-one and a difluorinated benzo-seven-membered heterocycle via the Schmidt rearrangement reaction. Compound 3g exhibited potent inhibitory effect on HCT116 cancer cells, making it a promising lead compound for further optimization and evaluation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Physical
Harpreet Singh Gujral, Gurwinder Singh, Jae Hun Yang, C. I. Sathish, Jiabao Yi, Ajay Karakoti, Mohammed Fawaz, Kavitha Ramadass, Ala'a H. Al-Muhtaseb, Xiaojiang Yu, Mark B. H. Breese, Ajayan Vinu
Summary: Transition metal nitrides have attracted much attention due to their unique structure and electrical properties, and they have great potential for electrocatalytic applications. This study successfully synthesized highly crystalline and mesoporous titanium carbonitride (MTiCN) materials using a combination of reactive templating approach and doping. The optimized MTiCN material exhibited considerable electrocatalytic hydrogen evolution reaction (HER) activity, which is close to the performance of commercial platinum/carbon catalysts. This work provides a simple solution for the rational design of porous transition metal carbon nitrides with excellent electrocatalytic properties.
Article
Chemistry, Physical
Yicheng Ye, Qiaohong Zhang, Guoying Weng, Zhuwei Zhu, Zhenguo Lyu, Chen Chen
Summary: The research introduced a simplified reverse-phase microemulsion method to introduce a high content of alkylamino and n-propyl on the surface of SiO2 nanospheres, resulting in the formation of surface nano-bulges and exposure of a high ratio of silicon species. The abundant surface groups enabled the material to exhibit high catalytic performance and achieve high conversion in the Aldol condensation reaction.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Organic
Revannath L. Sutar, Nikita Erochok, Stefan M. Huber
Summary: A series of cationic monodentate and bidentate iodo(benz)imidazolium-based halogen bond donors were employed as catalysts in a Mukaiyama aldol reaction. The bidentate XB donor showed strong performance even with low loading, while PF6 or OTf salts were inactive or showed background reaction through Lewis base catalysis. The stability of the catalyst over three consecutive cycles was confirmed through repetition experiments.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Hai-Hua Lu, Kang-Ji Gan, Fu-Qiang Ni, Zhihan Zhang, Yao Zhu
Summary: The concise total synthesis of salimabromide was achieved using a series of novel reactions, which allowed for the construction of its unique carbon skeleton and stereocenters.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Yanping Li, Ke Pan, Yougen Chen
Summary: A new type of degradable poly(beta-trimethylsilyloxy ester) was synthesized by the organocatalyzed Mukaiyama aldol polyaddition. These polyesters showed degradation behavior in the presence of nucleophiles, and the degradation mechanism was influenced by the nature of the catalyst used.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Michael Brizes, Jee-Yee Chen, Hannah Pineault, Nicholas A. Brunelli
Summary: Mesoporous silicas are complex yet ideal systems that can be functionalized with aminosilanes to produce highly active catalysts. In this study, common mesoporous silicas were functionalized and the per site catalytic activity was determined. Each material has four different types of sites, and despite their different pore structures and sizes, they have similar types of sites.
APPLIED CATALYSIS A-GENERAL
(2023)
Article
Nanoscience & Nanotechnology
Manas K. Bhunia, Debraj Chandra, Hitoshi Abe, Yasuhiro Niwa, Michikazu Hara
Summary: This study investigates the reductive amination of carbonyls to primary amines using heterogeneous catalysts containing earth-abundant metals. The researchers find that a nickel catalyst with mixed oxidation states shows high activity under low temperature and H-2 pressure, likely due to the formation of partially oxidized nickel nanoparticles homogeneously anchored onto silica. The stabilization of these nanoparticles through strong metal support interaction via electron donation from the metal to support is identified as a key factor. The study opens up a new avenue for the rational development of efficient catalysts for organic transformations under mild reaction conditions.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Nanoscience & Nanotechnology
Eri Hayashi, Takatoshi Tamura, Takeshi Aihara, Keigo Kamata, Michikazu Hara
Summary: Heterogeneously catalyzed aerobic oxidative C-H functionalization under mild conditions was achieved using nanosized murdochite-type oxide Mg6MnO8 (Mg6MnO8-MA) synthesized by the sol-gel method. The catalyst exhibited superior catalytic performance and could be reused several times without significant loss of activity. The mechanism of hydrogen atom transfer was found to be controlled by basicity, with O-2 activation playing a crucial role in the oxidation process.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Physical
Fei Han, Han Sun, Zhenchao Zhao, Yaxin Xu, Hong Dong, Weiwei Liu, Lu Sun, Zhili Wang, Guangjin Hou, Masaaki Kitano, Wei Li, Meiqing Shen, Haijun Chen
Summary: In this study, an environmentally friendly deNO(x) method using methanol as a reductant and pure H-FER zeolite as the catalyst was proposed. The metal-free zeolite showed nearly 4 times higher activity compared to commonly used precious metal catalysts. It exhibited comparable deNO(x) efficiency with state-of-the-art NH3-SCR on vanadium-based catalysts, along with good stability and potential for industrial application.
Article
Chemistry, Multidisciplinary
Masayoshi Miyazaki, Kiya Ogasawara, Takuya Nakao, Masato Sasase, Masaaki Kitano, Hideo Hosono
Summary: In this study, heavily H-doped BaTiO(3-x)Hx was used as an efficient and water-durable catalyst support for Pd nano-particles in liquid-phase hydrogenation reactions. The BaTiO(3-x)Hxoxyhydride with a hexagonal crystal structure exhibited metallic properties and showed high catalytic activity for the selective hydrogenation of unsaturated C-C bonds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Satomi Shibata, Keigo Kamata, Michikazu Hara
Summary: LaFeO3 nanoparticles synthesized using aspartic acid as a sol-gel method exhibit efficient and stable heterogeneous catalytic activity for the oxidative transformation of alpha-bromostyrene to phenacyl bromide under mild conditions without the need for additives and light irradiation. Changing the A-site metal cation from alkaline metals to lanthanum significantly improves the stability of Fe-containing perovskite oxides. LaFeO3 shows higher catalytic activity compared to other Fe3+/Fe2+-containing simple oxides, and the reaction proceeds through a radical-type mechanism involving surface adsorbed O-2 species over p-type LaFeO3.
Article
Chemistry, Multidisciplinary
Maki Koutani, Eri Hayashi, Keigo Kamata, Michikazu Hara
Summary: This study successfully synthesized mesoporous todorokite-type manganese oxide (OMS-1) nanoparticles with high specific surface areas using a new synthesis approach. It was found that there is a linear correlation between the catalytic performance and the surface area of the nanoparticles, without a trade-off relationship between particle size and catalytic activity. The OMS-1 nanoparticles exhibited high catalytic activity for the oxidation reactions and can be used as recyclable heterogeneous catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Shyamal Roy, Dilip Kumar Mondal, Sauvik Chatterjee, Avik Chowdhury, Tuhin Suvra Khan, M. Ali Haider, Subhash Mandal, Debraj Chandra, Michikazu Hara, Asim Bhaumik
Summary: In this study, a novel catalyst was synthesized via excess solution impregnation, which can selectively reduce CO2 into methane. The research found that under appropriate process conditions, the catalyst achieved a high CO2 conversion efficiency.
MOLECULAR CATALYSIS
(2022)
Article
Nanoscience & Nanotechnology
Takeshi Aihara, Wataru Aoki, Shin Kiyohara, Yu Kumagai, Keigo Kamata, Michikazu Hara
Summary: In this study, perovskite oxide nanoparticles were successfully synthesized using dicarboxylic acids as reagents. The resulting SrTiO3 nanoparticles showed high catalytic activity for the cyanosilylation of carbonyl compounds, even without a heat pretreatment.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Masashi Hattori, Natsuo Okuyama, Hiyori Kurosawa, Michikazu Hara
Summary: The Haber-Bosch process is required to produce ammonia without using fossil fuels in order to reduce global CO2 emissions. It is crucial to develop heterogeneous catalysts that can synthesize ammonia at temperatures below 100-150 degrees C to minimize energy consumption. In this study, metallic iron particles combined with an electron-donating material were used as a catalyst for ammonia synthesis, showing a high turnover frequency compared to other transition metals. This is attributed to the intrinsic desorption of hydrogen atoms from iron at low temperatures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Akihiko Kudo, Yoshihisa Sakata, Junko N. Kondo, Michikazu Hara, Jun Kubota, Shigeru Ikeda, Tsuyoshi Takata, Ryu Abe, Atsushi Takagaki, Takashi Hisatomi
Summary: Professor Kazunari Domen has focused on the research of catalysis, including the development of various photocatalysts, such as layered oxide and oxynitride photocatalysts, as well as oxysulfide photocatalysts with visible-light response. He has also explored water splitting using mechanocatalysis with metal oxides suspended in distilled water. In addition, Professor Domen has advanced the understanding of catalytic mechanisms through spectroscopic techniques such as transmission infrared spectroscopy and interfacial sum-frequency spectroscopy. Furthermore, he has investigated the use of carbon-based and layered solid acid materials as efficient catalysts.
Article
Chemistry, Physical
Aoi Matsuda, Kazuhiko Obara, Atsushi Ishikawa, Meng-Hsuan Tsai, Chia-Hsin Wang, Yu-Chuan Lin, Michikazu Hara, Keigo Kamata
Summary: The direct oxidation of methane to formaldehyde using molecular oxygen as the sole oxidant was studied over different bismuth-based catalysts. Among the catalysts tested, monoclinic BiPO4 nanoparticles synthesized in a mixed solvent of diethylene glycol (DEG) and water showed the highest catalytic activity and selectivity for formaldehyde formation.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Masashi Hattori, Natsuo Okuyama, Hiyori Kurosawa, Michikazu Hara
Summary: The Haber-Bosch process is used to produce ammonia for over 5 billion people, but now it is required to be produced without the use of fossil fuels to reduce global CO2 emissions by 3% or more. It is crucial to develop heterogeneous catalysts for ammonia synthesis below 100-150 degrees C to minimize energy consumption. This paper reports metallic iron particles combined with an electron-donating material as a catalyst for ammonia synthesis, which can catalyze ammonia synthesis even at 100 degrees C. The iron catalyst exhibits a high turnover frequency and can desorb adsorbed hydrogen atoms as hydrogen molecules at low temperatures.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Keigo Kamata, Nanami Kinoshita, Maki Koutani, Ryusei Aono, Eri Hayashi, Michikazu Hara
Summary: Beta-MnO2 nanoparticles with high specific surface areas were synthesized successfully and exhibited excellent catalytic activity and selectivity in the oxidation reaction of aromatic and heteroaromatic alcohols. The catalyst could also be used for the one-pot synthesis of nitriles and amides in the presence of ammonia, without the need for additional additives.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Kahoko Kato, Dian Deng, Yusuke Kita, Keigo Kamata, Michikazu Hara
Summary: Heterogeneous transition metal catalysts play an important role in the selective synthesis of primary amines. We have discovered a composite material composed of metallic cobalt and silica particles, which exhibits high catalytic performance under mild conditions and addresses the selectivity issues in the production of secondary and tertiary amines. Mechanistic studies revealed that the substrate nitrile and the product amine hinder the hydrogenation of secondary imine intermediates, resulting in a selective reaction. Additionally, the addition of coordinating organic molecules further improves the selectivity for primary amines.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Chemistry, Physical
Endah Suarsih, Yusuke Kita, Keigo Kamata, Michikazu Hara
Summary: A MgO-co-deposited Co catalyst is more efficient in promoting the alpha-alkylation of ketones with alcohols through a borrowing hydrogen mechanism compared to a Ru-based catalyst. Controlled experiments revealed that MgO promoted the hydrogenation step and the TiO2 support contributed to the condensation step in the reaction sequence.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
