Article
Chemistry, Organic
Kaijie Wei, Siyu Liang, Tonghao Yang, Wei Yu
Summary: In this study, a novel iron-catalyzed skeleton rearrangement of alkyl azides was reported. The reaction proceeds through a series of steps to generate the desired product in good yield.
Article
Chemistry, Inorganic & Nuclear
Yufang Xie, Qiyi Miao, Wenhao Deng, Yilei Lu, Yinuo Yang, Xiaohui Chen, Rong-Zhen Liao, Shengfa Ye, Chen-Ho Tung, Wenguang Wang
Summary: A diamido-bridged dicobalt complex supported by a diamidonaphthalene ligand, Cp*Co2(2)(mu-1,8-C10H8(NH)(2)) (1), was synthesized and its reactivity towards redox transformations of the Co2N2 core was investigated. It was found that the Co(II)-Co(II) bond can be protonated, resulting in the formation of a bridging hydride [1H](+). The diamidonaphthalene ligand stabilizes the Co(II)Co(III) mixed-valent state (1(+)), which can bind CO to form [1-CO](+). Surprisingly, the mixed-valent complex also activates H2O to give a Co(III)Co(III) hydroxy complex [1-OH](+), accompanied by the release of H2.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Eunjae Chung, Suho Kim, Amitava Rakshit, Pargat Singh, Jaewook Park, Taejoo Jeong, In Su Kim
Summary: In this study, the rhodium(III)-catalyzed C8-spiroannulation of 1-aminonaphthalenes with maleimides is investigated. The resulting C8-alkenylated 1-aminonaphthalenes can further react with nucleophilic 1-amino groups through intramolecular aza-Michael reaction, leading to the formation of spirofused tetracyclic frameworks. This method demonstrates a broad substrate scope and compatibility with various functional groups.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Zheng-Hai Wang, Dong-Hui Wang
Summary: A Cu-catalyzed straightforward synthesis of benzoxazoles from free phenols and cyclic oxime esters is reported, with moderate to good yields under mild reaction conditions. Large-scale syntheses of Ezutromid and Flunoxaprofe are demonstrated in one or two steps. The proposed catalytic mechanism involves Cu-catalyzed amination via inner-sphere electron transfer and consequent annulation.
Article
Chemistry, Multidisciplinary
Wowa Stroek, Martin Keilwerth, Daniel M. Pividori, Karsten Meyer, Martin Albrecht
Summary: The synthesis of N-heterocycles is crucial for the pharmaceutical industry, and a greener alternative using direct intramolecular C-H amination has been explored. A new iron-based complex catalyst was developed in this study, which can catalyze reactions without the need for protecting groups and achieved a significantly higher turnover number compared to other reported systems.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Applied
Rosella M. O'Mahony, Denis Lynch, Katie S. O'Callaghan, Stuart G. Collins, Anita R. Maguire
Summary: This study demonstrates the generation of tosyl azide in acetonitrile in flow under water-free conditions using an azide resin, and its use in diazo transfer to a series of aryl acetates. Successful telescoping with a rhodium acetate-catalyzed O-H insertion has been achieved, presenting a cleaner process compared to traditional batch conditions. The use of azide resin offers safety advantages and complements earlier protocols for tosyl azide generation in flow.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2021)
Editorial Material
Chemistry, Multidisciplinary
Dipankar Sahoo, Diana A. Iovan
Summary: A recent study reported the isolation and characterization of an N-trifluoromethyl-substituted Fe(IV) bisimido species that undergoes intramolecular C-H activation. This discovery opens up new possibilities for N-group-transfer chemistry.
Review
Chemistry, Organic
Jyoti M. Honnanayakanavar, Owk Obulesu, Surisetti Suresh
Summary: Copper-catalyzed N-arylation plays a crucial role in the total syntheses of therapeutic molecules, while the construction of fused N-heterocycles remains a vibrant area of research. Tandem reactions offer a convenient way to access complex organic molecules by reducing synthetic steps.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Li He, Yihang Zhu, Yongjun Xu
Summary: A copper-catalyzed direct C-H bond C5-amidation of 8-amidoquinolines with NFSI has been developed, which does not require any ligands and can form various derivatives in moderate to excellent yields using a commercially available Cu(II) catalyst under simple conditions. A single-electron transfer (SET)-mediated mechanism was proposed based on experimental data and a series of mechanistic studies.
Article
Chemistry, Organic
Yigao Tao, Rong Hu, Zeyu Xie, Ping Lin, Weiping Su
Summary: This work describes the development of an unprecedented cobalt-catalyzed para-selective amination of azobenzenes, which demonstrated the concept of electrophilic activation of the arene ring toward SNArH through coordination of the substituent on the arene ring to the metal catalyst. The reaction showed broad substrate scope, good yields, and regioselectivity for para-amination.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Andrea Geraci, Uros Stojiljkovic, Kevin Antien, Nihad Salameh, Olivier Baudoin
Summary: Chiral 1,2-diamines are important structures in bioactive natural products, active pharmaceutical ingredients, ligands for asymmetric catalysis, and organocatalysts. However, constructing chiral 1,2-diamine motifs is still challenging. To address this, researchers developed an iridium(III)-catalyzed intermolecular C(sp3)-H amidation reaction using a new and cleavable exo-protecting/directing group. This method allows for the synthesis of scalemic free 1,2-diamines from easily accessible precursors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Camilla Loro, Letizia Molteni, Marta Papis, Egle M. Beccalli, Donatella Nava, Leonardo Lo Presti, Stefano Brenna, Gioele Colombo, Francesca Foschi, Gianluigi Broggini
Summary: A novel synthetic strategy for the direct synthesis of oxazolo-phenoxazine compounds has been achieved through a dimerization/cyclization reaction of 2-benzylamino-phenols. Regioselective formation of 1-benzyl-2-phenyl-6-(aryl-benzyl)amino-benzimidazoles has also been demonstrated using specific starting substrates. The fluorescence emission properties of the synthesized products have been evaluated.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Po-Chun Yang, Kuan-Po Yu, Chi-Tien Hsieh, Junjie Zou, Chia-Te Fang, Hsin-Kuan Liu, Chih-Wen Pao, Liang Deng, Mu-Jeng Cheng, Chun-Yi Lin
Summary: High-spin, late transition metal imido complexes have attracted significant interest due to their group transfer reactivity and catalytic C-H activation of organic substrates. The resonance delocalization of the imido radical onto the mesityl ring significantly increases stability and reduces reactivity towards hydrogen atom transfer reagents.
Article
Chemistry, Multidisciplinary
Yan-Na Ma, Yan Gao, Yubin Ma, Yan Wang, Huazhan Ren, Xuenian Chen
Summary: Amination of carboranes has significant potential in organic and pharmaceutical synthesis. In this study, a practical method for the regioselective formation of B-N bonds in o- and m-carboranes using Pd(II) catalysis in HFIP solvent under air atmosphere was developed. The role of silver salt and HFIP solvent in the reaction mechanism was investigated.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Dinesh Parshuram Satpute, Gargi Nikhil Vaidya, Shyam Kumar Lokhande, Sangita Dattatray Shinde, Shivkanya Madhavrao Bhujbal, Deep Rohan Chatterjee, Pooja Rana, Ashwini Venkatesh, Mithilesh Nagpure, Dinesh Kumar
Summary: The expansion of catalytic methods, particularly nickel-catalyzed reactions in aqueous media, offers cost-effective synthetic routes, but challenges related to the relative instability of nickel complexes in water still need to be overcome.
Article
Chemistry, Multidisciplinary
Yuma Morimoto, Yusaku Takagi, Toru Saito, Takehiro Ohta, Takashi Ogura, Norimitsu Tohnai, Motohiro Nakano, Shinobu Itoh
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2018)
Article
Chemistry, Inorganic & Nuclear
Sayantan Paria, Yuma Morimoto, Takehiro Ohta, Shinsuke Okabe, Hideki Sugimoto, Takashi Ogura, Shinobu Itoh
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2018)
Article
Chemistry, Organic
Roxanne Krug, Dennis Schroeder, Jan Gebauer, Sanel Suljic, Yuma Morimoto, Nobutaka Fujieda, Shinobu Itoh, Joerg Pietruszka
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2018)
Article
Chemistry, Multidisciplinary
Yuma Morimoto, Yuki Shimaoka, Yuri Ishimizu, Hiroshi Fujii, Shinobu Itoh
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Ikuma Shimizu, Yuma Morimoto, Gunasekaran Velmurugan, Tulika Gupta, Sayantan Paria, Takehiro Ohta, Hideki Sugimoto, Takashi Ogura, Peter Comba, Shinobu Itoh
CHEMISTRY-A EUROPEAN JOURNAL
(2019)
Article
Chemistry, Multidisciplinary
Daiki Fujita, Akira Kaga, Hideki Sugimoto, Yuma Morimoto, Shinobu Itoh
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2020)
Article
Chemistry, Inorganic & Nuclear
Yuma Morimoto, Shinichi Hanada, Ryusuke Kamada, Arisa Fukatsu, Hideki Sugimoto, Shinobu Itoh
Summary: The hydroxylation of cyclohexane was successfully achieved using an iron(III) complex supported by a trianionic planar tetradentate ligand, showing high turnover number and selectivity for alcohol production. The involvement of an iron(III) acyl peroxido complex as the reactive species was suggested by spectroscopic measurements, providing insight into the reaction mechanism.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Yuma Morimoto, Makito Kawai, Aya Nakanishi, Hideki Sugimoto, Shinobu Itoh
Summary: The coordination environment of copper(II) complexes plays a crucial role in determining the reactivity of their acylperoxide adduct complexes, as demonstrated by experimental and theoretical calculations in this study. The ligand-field-splitting energy increases with an increase of the ring size of the diamine moiety, enhancing the reactivity of the complexes. Different reactivities of the complexes with m-chloroperbenzoic acid (m-CPBA) are evaluated using density functional theory (DFT) calculations.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Tomoya Shinke, Mayu Itoh, Takuma Wada, Yuma Morimoto, Sachiko Yanagisawa, Hideki Sugimoto, Minoru Kubo, Shinobu Itoh
Summary: Mechanistic studies on alkane hydroxylation with m-CPBA catalyzed by nickel(II) complexes, Ni-II(L), have revealed the efficient catalytic activity of Ni-II(TPA) in oxidizing cycloalkanes and the first-order dependence of reaction rate on substrate and Ni-II(L) concentration. The significant kinetic deuterium isotope effect and different catalytic activity of Ni-II(L) supported by tetradentate ligands suggest the involvement of hydrogen atom abstraction in the rate-limiting step and the contribution of Ni-II(L) in the catalytic cycle, respectively. Possible contributions of (L)Ni-II-O-. and the aroyloxyl radical as reactive oxidants are discussed based on kinetic analysis and the effects of O-2 and CCl4 on product distribution pattern.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Yuma Morimoto, Shinobu Itoh
Summary: This article discusses the applications of hydroxylation reactions in both chemical and biological fields. By studying metalloenzymes in living organisms, we can understand how these enzymes achieve selective oxidation reactions of hydrocarbons. The article summarizes the achievements of our laboratory in designing highly selective and efficient oxidation reactions.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2022)
Article
Chemistry, Inorganic & Nuclear
Takuma Wada, Hideki Sugimoto, Yuma Morimoto, Shinobu Itoh
Summary: In this study, a series of nickel(II) complexes were synthesized and used for catalyzing the oxidation of alkanes with m-CPBA. It was found that the nickel(II) complex with a 6-membered cyclic diamine and (2-pyridyl)methyl sidearms showed the highest catalytic activity and selectivity.
Article
Chemistry, Inorganic & Nuclear
Yang Lan, Yuma Morimoto, Ikuma Shimizu, Hideki Sugimoto, Shinobu Itoh
Summary: Structures, physicochemical properties, and reactivity of a whole series of mononuclear copper(II)-halide complexes supported by a TMG(3)tach tridentate ligand have been investigated. The results demonstrate the importance of the ligand structure in determining the spectroscopic and electronic features as well as the reactivity towards C-H bond activation reaction. The bulky and strongly electron-donating TMG substituents enforce a tetrahedral geometry for the copper(II) complexes, resulting in specific optical and chemical properties.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Arisa Fukatsu, Yuma Morimoto, Hideki Sugimoto, Shinobu Itoh
CHEMICAL COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Tsukasa Abe, Yuta Hori, Yoshihito Shiota, Takehiro Ohta, Yuma Morimoto, Hideki Sugimoto, Takashi Ogura, Kazunari Yoshizawa, Shinobu Itoh
COMMUNICATIONS CHEMISTRY
(2019)