Article
Chemistry, Multidisciplinary
Mukulesh Mondal, Shubhanjan Mitra, Dylan J. Twardy, Manashi Panda, Kraig A. Wheeler, Nessan J. Kerrigan
Summary: This paper describes a versatile asymmetric synthesis of bicyclic pyrazolidinones through alkaloid-catalyzed formal [3+2]- and [3 + 2 + 2]-cycloadditions of ketenes with azomethine imines. The method shows good tolerance towards ketene and a variety of monosubstituted ketenes, with high yields and excellent diastereoselectivity and enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Sung Hyun Kang, Jaeeun No, Sung-Gon Kim
Summary: We have developed a catalyst-free [3 + 2]-cycloaddition reaction between N,N'-cyclic azomethine imines and c-hydroxy-a,b-unsaturated ketones at 60 degrees C. This reaction produces N,N'-bicyclic pyrazolidinones with high yields and remarkable diastereoselectivity. The reaction was also applied to b-substituted-a,b-unsaturated ketones and esters, providing a practical and efficient protocol for the synthesis of biologically relevant pyrazolidinone frameworks.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Akshay Subhash Narode, Rai-Shung Liu
Summary: A one-pot synthesis of 5,6-dihydroindolo[2,1-a]isoquinolines from gold-catalyzed annulations between N-(oalkynylphenyl)imines and alpha-diazo esters is described. This cascade reaction involves the attack of the diazo ester at the imine to form cis-aziridine, followed by stereoselective [3 + 3]-annulations with the tethered arylalkyne. This new catalysis has been utilized to prepare a bioactive molecule of 5,6-dihydroindolo[2,1-a]isoquinoline.
Article
Chemistry, Multidisciplinary
Chen Chen, Xing-Xing Yang, Zhi Zhao, Bo Han, Wei Du, Ying-Chun Chen
Summary: In this study, the normal 1,3-dipolar cycloaddition between the carbonates of 4-hydroxy-2-cyclopentenones and C,N-cyclic azomethine imines was switched to an inverse-electron-demand version under Pd(0) catalysis. This transformation was achieved by in situ generation of HOMO-raised eta(2)-Pd(0)-cyclopentadienone complexes. The researchers constructed a variety of fused heterocyclic architectures with high levels of diastereo and enantioselectivity. Furthermore, diastereodivergent synthesis was realized by tuning the bifunctional phosphine ligands. A similar reaction with in situ formed thiophene-1,1-dioxide was also compatible by using a chiral bisphosphine ligand, leading to the formation of fused cyclic sulfone frameworks with high stereoselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Shakil Ahmed, Atul Kumar, Partha Sarathi Mukherjee
Summary: An emissive Pt(II) coordination polymer (TBP) was successfully synthesized by assembling a benzothiadiazole-based Pt(II) acceptor (A) with a tetraphenylethene (TPE) containing donor (L). With multiple benzothiadiazole units, TBP showed excellent reactive oxygen species generation ability and acted as an efficient photocatalyst for oxidative coupling of benzylamine under visible light. It achieved full conversion within 2 hours at room temperature and demonstrated reusability for multiple cycles, along with easy separation of the product.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Hang Xu, Sho Yamaguchi, Takato Mitsudome, Tomoo Mizugaki
Summary: A copper-catalyzed system using copper nitride nanocubes as catalysts has been developed for the protosilylation reaction of unsaturated compounds. This method allows for the efficient production of organosilanes under mild and additive-free conditions.
Article
Chemistry, Multidisciplinary
James E. Baumann, Gojko Lalic
Summary: A new method for the differential dihydrofunctionalization of terminal alkynes has been developed, enabling the synthesis of allylic boronate esters through a reductive three-component coupling reaction. This transformation, promoted by a copper/palladium catalyst system, hydrofunctionalizes both pi-bonds of the alkyne. The method is compatible with a wide range of functional groups.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Jiacheng Li, Lorenzo Carli, Sara Helen Kyne, Philip Wai Hong Chan
Summary: This study presents an efficient method for the synthesis of 1,2-diamines through the 4CzPN-catalysed a-aminoalkylation of azomethine imines by secondary and tertiary a-silylamines under blue light emitting diode (LED) light (456 nm). Achieved without the use of metals or additives at room temperature, the synthetic protocol provides product yields up to 99% and can be applied to the late-stage functionalisation of three drug molecules and the gram-scale preparation of one example.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Christian Frabitore, Tom Livinghouse
Summary: This article presents a novel synthetic method for the production of saturated N-heterocyclic pharmacophore motifs, utilizing N,N-dimethylhydrazinoalkenes and diethylzinc followed by a Cu(I)-catalyzed cross-coupling reaction with 1-bromoalkynes to afford piperidines and pyrrolidines. The synthesis tolerates heteroatom-bearing alkynes and, unexpectedly, the use of ethyl propiolate as the trapping electrophile leads to selective N-functionalization with the formation of vinylogous urethanes. Alternative Cu(I) complexes were also evaluated as potential catalysts. This synthetic protocol can be easily scaled up for preparative purposes.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Nejc Petek, Helena Brodnik, Uros Groselj, Jurij Svete, Franc Pozgan, Bogdan Stefane
Summary: In this study, we report the photochemical transformation of pyrazolo[1,2-a]pyrazolone substrates under visible light irradiation, leading to homolytic C-N bond cleavage to produce NI-substituted pyrazoles. Additionally, chemoselective heterolytic C-N bond cleavage is observed in the presence of bromomalonate in the pyrazolo[1,2-a]pyrazole core.
Article
Biochemistry & Molecular Biology
Guipeng Feng, Guoyang Ma, Wenyan Chen, Shaohong Xu, Kaikai Wang, Shaoyan Wang
Summary: The [3 + 2] 1,3-dipolar cycloaddition of C,N-cyclic azomethine imines with allyl alkyl ketones has been achieved, resulting in a range of tetrahydroisoquinoline derivatives with good diastereoselectivities and enantioselectivities. The absolute configuration of the product was determined using quantum electronic circular dichroism calculation and ECD spectrum method.
Article
Chemistry, Physical
Ruixue Zhang, Yan Chen, Muhua Ding, Jie Zhao
Summary: This review provides a comprehensive summary of seminal heterogenized Cu-catalyzed homogenous catalysis reported over the last decade, highlighting the potential and synthetic perspectives of heterogeneous copper catalysis in both academic and industry.
Article
Chemistry, Multidisciplinary
Yuanteng Zhang, Yong Wu, Yaqiong Su, Yue Cao, Zhenjin Liang, Dali Yang, Ruohan Yu, Dongchao Zhang, Jinsong Wu, Wei Xiao, Aiwen Lei, Dong Gu
Summary: The study successfully synthesized an efficient CuN4/OMNC catalyst through a copper catalyzed strategy for selective oxidative crosscoupling of terminal alkynes, achieving high yields under mild conditions. The catalyst showed high selectivity in DFT calculations and can be easily separated and reused.
Article
Chemistry, Organic
Hai-Shan Jin, Ya-Zhen Du, Qing-Yang Zhao, Li-Ming Zhao
Summary: The first Ru(ii)-catalyzed cascade C-H activation/annulation reactions of N-aryl-pyrazolidinones with sulfoxonium ylides for the synthesis of cinnoline-fused pyrazolidinones have been reported. This transformation proceeds smoothly under simple conditions and a wide range of substrates were assessed, with products isolated in good to excellent yields (51% to 99%).
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Chemistry, Organic
Yoseop Kim, Seung Yeon Kim, Sung-Gon Kim
Summary: A new asymmetric annulation reaction was developed to efficiently synthesize enantioenriched polyheterotricyclic imidazolidines and oxazolidines.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Takuo Minato, Daniel Salley, Noritaka Mizuno, Kazuya Yamaguchi, Leroy Cronin, Kosuke Suzuki
Summary: An efficient stepwise synthesis method was developed to discover new heteromultinuclear metal clusters using a robotic workflow, resulting in the discovery of novel nonanuclear tetrametallic oxo clusters with single-molecule magnet properties. These clusters showed higher energy barriers for magnetization reversal compared to the parent cluster, demonstrating the potential for unique properties in designed multistep reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Yusuke Morino, Takafumi Yatabe, Kosuke Suzuki, Kazuya Yamaguchi
Summary: The efficient aerobic oxidative esterification of ethylene glycol to various oxalic acid diesters has been achieved using CuCl/tetramethylethylenediamine/1,5-dimethyl-9-azanoradamantane N-oxyl catalyst. The reaction shows high selectivity for ethylene glycol-derived alcohols/hemiacetals even in the presence of other aliphatic primary alcohols, and the efficient esterification is enabled by the preferential bidentate coordination of ethylene glycol-derived alcohols/hemiacetals to the Cu(ii) species.
Article
Chemistry, Multidisciplinary
Kang Xia, Takafumi Yatabe, Kentaro Yonesato, Tomohiro Yabe, Soichi Kikkawa, Seiji Yamazoe, Ayako Nakata, Kazuya Yamaguchi, Kosuke Suzuki
Summary: A feasible method was developed for preparing supported anionic gold nanoparticle catalysts using multivacant lacunary polyoxometalates, confirming the strong electronic interaction between gold nanoparticles and the polyoxometalates, allowing for sequential modulation of the electronic states of the catalysts. The catalyst prepared using [SiW9O34](10-) showed superior catalytic performance and stability compared to supported gold nanoparticle catalysts without this modification.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Yoshihiro Koizumi, Kentaro Yonesato, Kazuya Yamaguchi, Kosuke Suzuki
Summary: A novel approach was developed for the selective synthesis of several multinuclear copper-containing ring-shaped POMs in organic solvents, using methoxy groups as organic protecting ligands to control the number and arrangement of introduced metal cations.
INORGANIC CHEMISTRY
(2022)
Review
Chemistry, Multidisciplinary
Kang Xia, Kazuya Yamaguchi, Kosuke Suzuki
Summary: This article provides an overview of recent advances in hybrid materials composed of polyoxometalates (POMs) and metal nanoparticles. The properties and applications of these materials in various fields such as electrochemistry, photochemistry, and catalysis are discussed. The combination of these two classic inorganic materials enables cooperative and synergistic behavior, presenting new possibilities for future development in this field.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Takehiro Matsuyama, Takafumi Yatabe, Tomohiro Yabe, Kazuya Yamaguchi
Summary: A versatile 1,2-diketone decarbonylation to produce diaryl ketones was achieved using a CeO2-supported Au-Pd alloy nanoparticle catalyst. The high catalytic performance was attributed to the promotion of reductive elimination by electron-deficient Pd(0) species interacting strongly with CeO2 and the suppression of catalyst deactivation through Pd alloying with Au.
Article
Chemistry, Multidisciplinary
Takaaki Suzuki, Tomohiro Yabe, Keiju Wachi, Kentaro Yonesato, Kosuke Suzuki, Kazuya Yamaguchi
Summary: We developed a new preparation method to obtain highly dispersed metal-oxo cluster Cs salts via cation exchange from the corresponding TBA salts on supports. Various characterizations revealed that the method maintained the stability and structure of the metal-oxo clusters under high temperature and aerobic conditions.
Article
Chemistry, Multidisciplinary
Kentaro Yonesato, Daiki Yanai, Seiji Yamazoe, Daisuke Yokogawa, Takashi Kikuchi, Kazuya Yamaguchi, Kosuke Suzuki
Summary: In this study, a sequential synthesis method for structurally well-defined silver nanoclusters with exposed surfaces was developed using ring-shaped molecular metal oxides. These nanoclusters showed high catalytic activity for selective reduction reactions, making them promising in catalysis and energy conversion applications.
Article
Chemistry, Multidisciplinary
Hui Li, Takafumi Yatabe, Satoshi Takayama, Kazuya Yamaguchi
Summary: In this study, a highly selective synthesis of primary anilines from cyclohexanones and NH3 was achieved via an efficient acceptorless dehydrogenative aromatization heterogeneously catalyzed by an Mg(OH)(2)- supported Pd nanoparticle catalyst. The basic sites of the Mg(OH)(2) support effectively accelerate the acceptorless dehydrogenative aromatization, suppressing the formation of secondary amine byproducts. The deposition of Mg(OH)(2) species inhibits the adsorption of cyclohexanones on the Pd nanoparticles to suppress phenol formation, achieving the desired primary anilines with high selectivity.
Article
Chemistry, Multidisciplinary
Chifeng Li, Chen Gu, Kazuya Yamaguchi, Kosuke Suzuki
Summary: Photocatalytic polymer degradation is a promising solution to global plastic waste disposal. In this study, it was demonstrated that various polyesters and polyethers can be efficiently degraded in the presence of a polyoxometalate photocatalyst, specifically decatungstate (W10). The degradation efficiency of W10 was notably higher than previously reported photocatalysts.
Article
Chemistry, Multidisciplinary
Soichi Kikkawa, Shoji Fukuda, Jun Hirayama, Naoki Shirai, Ryo Takahata, Kosuke Suzuki, Kazuya Yamaguchi, Toshiharu Teranishi, Seiji Yamazoe
Summary: A catalyst with specific base and reduction abilities was prepared by modifying the surface of Au nanoparticles with [Nb6O19](8-) clusters on Al2O3. This dual functional catalyst efficiently reduced p-nitrophenol to p-aminophenol using H-2 as a reductant. The surface modification strategy was also applicable to the reduction of other nitro compounds.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Kentaro Yonesato, Seiji Yamazoe, Soichi Kikkawa, Daisuke Yokogawa, Kazuya Yamaguchi, Kosuke Suzuki
Summary: The properties of metal nanoclusters depend on their structures and electronic states. However, controlling the electronic states is still challenging. Recently, we achieved reversible control of the electronic states of atomically precise Ag nanoclusters by utilizing the acid/base nature of polyoxometalates as inorganic ligands.
Article
Chemistry, Multidisciplinary
Daisuke Takei, Takafumi Yatabe, Tomohiro Yabe, Ray Miyazaki, Jun-ya Hasegawa, Kazuya Yamaguchi
Summary: This study investigates the catalytic active site structure, mechanism, and C-H bond activation process of Pd-Au bimetallic nanoparticle catalyst supported on CeO2 for the selective aerobic alpha,beta-dehydrogenation of saturated ketones. Experimental and computational results reveal that a Pd(II)-(mu-O)-Au(0) structure is the true active site for this reaction, where the Pd atom acts as a Lewis acid and the adjacent mu-oxo species acts as a Bronsted base simultaneously.
Article
Chemistry, Multidisciplinary
Chifeng Li, Kazuya Yamaguchi, Kosuke Suzuki
Summary: The selective synthesis of a tetranuclear vanadium-containing phosphomolybdate was achieved by using a pyridine-protected template, addressing the issue of randomly distributed isomers and undesirable impurities generated during the traditional one-pot synthesis in aqueous media.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Takehiro Matsuyama, Takafumi Yatabe, Tomohiro Yabe, Kazuya Yamaguchi
Summary: This study reports a versatile decarbonylation of diaryl 1,2-diketones to afford diaryl ketones using a CeO2-supported Au-Pd alloy nanoparticle catalyst. Through thorough characterization of the catalyst, kinetic evaluation, and control experiments, it was found that the high catalytic performance is attributed to the interaction of electron-deficient Pd(0) species with CeO2 and the suppression of catalyst deactivation by alloying Pd with Au.
