Article
Chemistry, Applied
Hongyun Qin, Jianjing Yang, Kelu Yan, Yaxuan Xue, Meichen Zhang, Xuejun Sun, Jiangwei Wen, Hua Wang
Summary: An efficient electrochemical hydrogenation strategy has been developed to convert electron-deficient internal olefins and alkynes to saturate ketones, with the capability of easy scaling up and good efficiency. Mechanistic studies show the involvement of radical hydrogenation in this transformation.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
George Hutchinson, Calum D. M. Welsh, Jordi Bures
Summary: FTIR spectroscopy is a common in situ reaction monitoring technique, but to quantify the data, precalibration or offline analyses are required. The use of standard addition offers a convenient method for obtaining quantitative FTIR data.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Haotian Chen, Samuel Barton, Minjun Yang, Rosalind E. M. Rickaby, Heather A. Bouman, Richard G. Compton
Summary: A combination of fluoro-electrochemical microscopy and neural network technology can accurately distinguish different taxonomies of marine phytoplankton, providing a flexible and highly accurate solution for phytoplankton classification and autonomous ocean monitoring.
Article
Chemistry, Organic
Pengwei Hu, Lin Guo, Lulu Zhao, Chao Yang, Wujiong Xia
Summary: An intermolecular alkene dicarbofunctionalization via electrochemical reduction that combines alkyl and aryl iodides with styrene derivatives was successfully achieved. The multicomponent reaction exhibited several advantages such as simplicity, versatility, and scalability. Mechanistic investigations provided evidence for the electrochemical nickel catalytic cycle and the formation of alkyl radical species from alkyl iodides.
Article
Chemistry, Applied
Cong Jiang, Yujie Liao, Heng Li, Sumin Zhang, Ping Liu, Peipei Sun
Summary: A practical electrochemical Minisci-type reaction was developed for the synthesis of silylated heterocycles. By using N-hydroxyphthalimide (NHPI) as the hydrogen atom transfer (HAT) catalyst and trialkylsilanes as the silyl radical sources, various electron-deficient heterocycles, such as quinoline, quinoxaline, phthalazine, 3,6-dichloropyridazine, phenanthridine, 6-chloroimidazo[1,2-b]pyridazine, and coumarin, could be easily transformed into the corresponding silylated products in yields of 37-83%.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Maude Aelterman, Philippe Jubault, Thomas Poisson
Summary: This paper reveals the electrochemical borylation of electro-deficient alkenes and allenoates. A variety of Michael acceptor and allenoates easily reacted in an undivided cell under galvanostatic conditions. The reaction offers an access to versatile borylated building blocks with good to excellent yields (20 examples, 47% to 91% yields). A plausible reaction mechanism, based on the literature precedent, was suggested.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Biswajita Baruah, Mohit L. Deb
Summary: This review highlights the applications of organozinc reagents in conjugate addition reactions, showcasing their advantages over other organometallic reagents. The conjugate addition of organozinc has been widely studied for its effectiveness in organic synthesis and compatibility with various functional groups, making it a crucial strategy for synthetic chemists. Despite the availability of some reviews, a comprehensive review focusing specifically on organozinc reagents and their role in conjugate addition reactions is deemed important for organic researchers.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Lin Wang, Yingnan Liu, Zhengfei Chen, Qizhou Dai, Chung-Li Dong, Bin Yang, Zhongjian Li, Xiaobing Hu, Lecheng Lei, Yang Hou
Summary: In this study, a novel Ru-based catalyst Ru/Ni@C with outstanding hydrogen evolution reaction (HER) performance was developed. It exhibited an ultra-low overpotential of 309 mV at 1.0 A cm-2, surpassing commercial Pt/C and Ru/C catalysts. Experimental and theoretical results showed that efficient electron transfer from anchored Ru cluster to core Ni particles via carbon layer led to the formation of electron-deficient Ru site, which benefited the adjustment of H adsorption ability and ultimately promoted the whole HER process.
Article
Chemistry, Organic
Xuan Zhan, Guiqi Gao, Yating Liang, Fengyi Li, Ke Liu, Weigang Fan, Sheng Zhang, Man-Bo Li
Summary: Herein, we report a 'green' aminochlorination method of alkenes using acetonitrile and MgCl2 as nitrogen and chlorine sources, respectively. Benzimidazole was used as a reactivity modulator for chlorine radicals, achieving tunable reactivity, chemoselectivity and stereoselectivity in the four-component reaction.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Shuaiyu Ji, Lixing Zhao, Bingyang Miao, Meng Xue, Tao Pan, Zhichao Shao, Xin Zhou, Aiping Fu, Yuexia Zhang
Summary: In this study, we reported the electrochemical activation of nitromethane to construct isoxazoline aldoximes, using nitromethane as both the heterocyclic skeleton and oxime sources. The isoxazoline aldoximes were synthesized in a single step from low-cost nitromethane and olefins, with moderate to excellent yields. The reaction showed high atom-economy and E-selectivity. Mechanistic studies revealed that under electrochemical conditions, nitromethane could be activated to generate a 1,2,5-oxadiazole 2-oxide intermediate, which underwent [3+2] cycloaddition with olefins to yield isoxazoline aldoximes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Satsuki Shigenaga, Haruko Shibata, Koto Tagami, Tadashi Kanbara, Tomoko Yajima
Summary: The eosin Y-catalyzed hydroperfluoroalkylation of electron-deficient alkenes is a selective and efficient reaction that proceeds smoothly under visible light irradiation. This reaction allows for the use of various perfluoroalkyl bromides and electron-deficient olefins, and all required chemicals are readily available and safe.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Dongqiu Li, Fang Cheng, Yuhai Tang, Jing Li, Yang Li, Jiao Jiao, Silong Xu
Summary: The method described involves a phosphine-catalyzed internal redox [4 + 2] annulation of 1,4-enynoates with electron-deficient alkenes, resulting in the efficient synthesis of highly functionalized cyclohexenes with exclusive regioselectivity and high diastereoselectivity under mild conditions.
Article
Biochemistry & Molecular Biology
Zhen-Hua Wang, Tong Zhang, Li-Wen Shen, Xiu Yang, Yan-Ping Zhang, Yong You, Jian-Qiang Zhao, Wei-Cheng Yuan
Summary: Cycloaddition reactions between heteroaromatic N-ylides and electron-deficient olefins have been developed. The N-ylides, generated in situ from N-phenacylbenzothiazolium bromides, react smoothly with maleimides under mild conditions to yield fused polycyclic octahydropyrrolo[3,4-c]pyrroles in high yields. This reaction concept can also be extended to 3-trifluoroethylidene oxindoles and benzylidenemalononitriles, enabling the synthesis of highly functionalized polyheterocyclic compounds. A gram-scale experiment was carried out to demonstrate the practicality of the methodology.
Article
Chemistry, Organic
Yi Yu, Shao-Fen Wu, Xiao-Bin Zhu, Yaofeng Yuan, Zhen Li, Ke-Yin Ye
Summary: Electrochemical sulfoxidation reaction is a highly selective reaction that can be carried out with thiols and alkyl halides as starting materials in a single operation.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zenghui Ye, Rongjin Zhu, Feng Wang, Haobin Jiang, Fengzhi Zhang
Summary: Atom- and step-economic oxo-azidation and oxo-hydroxyphthalimidation of styrenes were developed under mild electrolytic conditions, leading to efficient synthesis of valuable alpha-azido or hydroxyphthalimide aromatic ketones from readily available starting materials. Mechanism studies revealed two different pathways involved in these transformations.
Article
Polymer Science
Tomoyuki Kurioka, Takahiro Komamura, Naoki Shida, Teruaki Hayakawa, Ikuyoshi Tomita, Shinsuke Inagi
Summary: The ordered structure of poly(3-(2-ethylhexyl)thiophene) (P3EHT) films can be controlled by changing the solvent used to prepare them. The successful electrochemical post-functionalization (ePF) of P3EHT films is attributed to their greater electrochemical conductivity compared to amorphous P3EHT films.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2022)
Article
Polymer Science
Alvin Tanudjaja, Ryoyu Hifumi, Shinsuke Inagi, Ikuyoshi Tomita
Summary: In this study, an organometallic polymer monomer containing fused metallacyclic building block was successfully synthesized. By controlling the synthesis conditions, a black-colored polymer with good solubility in organic solvents and stability was obtained, and its optical properties were investigated.
Article
Electrochemistry
Hiroki Sakagami, Hiroaki Takenaka, Suguru Iwai, Naoki Shida, Elena Villani, Akihiro Gotou, Tomohiro Isogai, Akiyoshi Yamauchi, Yosuke Kishikawa, Toshio Fuchigami, Ikuyoshi Tomita, Shinsuke Inagi
Summary: The study introduces an advanced process combining flow reactors and bipolar electrochemistry, which successfully achieved anodic fluorination and anodic coupling of organic compounds under low concentration of supporting electrolytes. This combined system holds promise as a prospective electrosynthesis method, aligning with the development direction of green and sustainable chemistry.
Article
Chemistry, Analytical
Yulin Shi, Elena Villani, Yequan Chen, Yaqian Zhou, Zhenghao Chen, Altaf Hussain, Guobao Xu, Shinsuke Inagi
Summary: Bipolar electrochemistry has gained renewed interest as an effective approach for materials synthesis due to its unique features compared to conventional electrochemistry, such as wireless electrode reactions and gradient potential distribution. In this study, we report the high-throughput electrosynthesis of gradient polypyrrole films using a new electrochemical cell design called the single-electrode electrochemical system (SEES). The SEESs consist of multiple microelectrochemical cells attached to an indium tin oxide electrode, allowing for parallel electrochemical reactions to be carried out simultaneously and controlled by a single electrode. The use of SEES has been shown to be a convenient and cost-effective strategy for high-throughput electrosynthesis and has opened up a new approach for rapid condition screening in gradient film preparation.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Analytical
Tomoki Hirohata, Susumu Kawauchi, Ikuyoshi Tomita, Shinsuke Inagi
Summary: This paper investigates the electrochemical reduction behavior of the new redox-active hexagonal macrocycle pillar[6]quinone (P[Q]6) in the presence of Li+ ions dissolved in an aprotic solvent using density functional theory calculations. The results show that the electrostatic repulsion between quinone units determines the multi-electron reduction behavior of P[Q]6, which is consistent with the voltammetric measurements. The lithiation process involves bridging of adjacent carbonyl groups by Li+ ions and the formation of coordination bonds outside the macrocycle, and the calculated lithiation potentials correspond to the voltammogram waveform. Preliminary calculations involving two macrocycles confirm intermolecular lithium coordination. These findings enhance our understanding of the electrochemical properties of P[Q]6 and its potential application in redox materials.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hideyuki Nojima, Takashi Shimoda, Shinsuke Inagi, Toshio Fuchigami
Summary: Various anodic substitution reactions, including fluorination, methoxylation, acetoxylation, and cyanation, of heteroatom compounds containing sulfur or nitrogen were comparatively studied using boron-doped diamond (BDD), Pt, and glassy carbon (GC) anodes. It was found that BDD anode, similar to Pt anode, is highly effective for these reactions despite both BDD and GC electrodes being carbon-based materials.
ISRAEL JOURNAL OF CHEMISTRY
(2023)
Article
Electrochemistry
Toshiyasu Fujita, Shinsuke Inagi, Toshio Fuchigami
Summary: Anodic oxidation of PhTeR (R = CF3CH2, CF2H, Me, Ph) was performed in methanol with various supporting electrolytes (YO- M+) such as p-tosylate, benzenesulfonate, acetate, and benzoate salts using a divided cell, yielding predominantly monomeric PhRTe(OY)(2) and dimeric PhR(OY)Te-O-TePhR(OY) compounds in moderate to good yields.
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Zhenghao Chen, Yaqian Zhou, Elena Villani, Naoki Shida, Ikuyoshi Tomita, Shinsuke Inagi
Summary: Recently, it has been found that poly(3,4-ethylenedioxythiophene) (PEDOT) fibers can be produced from bipolar electrodes in acetonitrile solution using alternating current (AC)-bipolar electro-polymerization. This study extends this method to ionic liquid (IL) media and explores the growth of PEDOT fibers in three different ILs. The obtained PEDOT morphologies were found to be influenced by the physicochemical properties of the ILs.
Article
Chemistry, Organic
Yushi Ohno, Shogo Ando, Daisuke Furusho, Ryoyu Hifumi, Yuuya Nagata, Ikuyoshi Tomita, Shinsuke Inagi
Summary: Here, a facile and selective synthesis of cationic azatriphenylene derivatives was achieved through electrochemical intramolecular cyclization, where the key step involves atom-economical C-H pyridination without a transition-metal catalyst or an oxidant. This proposed strategy provides a practical approach for introducing cationic nitrogen (N (+)) into pi-electron systems, thus expanding the molecular design of N (+)-doped polycyclic aromatic hydrocarbons.
Article
Chemistry, Multidisciplinary
Tomoki Shirokura, Tomoki Hirohata, Kosuke Sato, Elena Villani, Kazuyasu Sekiya, Yu-An Chien, Tomoyuki Kurioka, Ryoyu Hifumi, Yoshiyuki Hattori, Masato Sone, Ikuyoshi Tomita, Shinsuke Inagi
Summary: We report a novel synthetic methodology that utilizes an electrogenerated acid (EGA) as an effective Bronsted acid catalyst for imine bond formation and provides the corresponding COF film deposited on the electrode surface. The COF structures obtained with this method exhibited high crystallinities and porosities, and the film thickness could be controlled. Furthermore, this process was applied for the synthesis of various imine-based COFs, including a three-dimensional (3D) COF structure.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Materials Science, Multidisciplinary
Elena Villani, Yanyun Zhang, Zhenghao Chen, Yaqian Zhou, Mariko Konishi, Ikuyoshi Tomita, Shinsuke Inagi
Summary: In this study, we developed poly(3,4-ethylenedioxythiophene)(PEDOT) thin films and their composites, such as PEDOT-copper (PEDOT-Cu) and PEDOT-polythiophene (PEDOT-PT), on a nonconductive substrate using AC-bipolar electropolymerization. These films were then utilized as wireless electrodes for the generation of luminol electrochemiluminescence (ECL). The intensity and spatial distribution of the ECL light emission were found to be correlated with the conductivity and composition of the different polymer films.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Polymer Science
Yoshimasa Matsumura, Alvin Tanudjaja, Mizuki Fukushima, Makoto Higuchi, Shin Ogino, Makoto Ishidoshiro, Yasuyuki Irie, Hiroaki Imoto, Kensuke Naka, Ryoyu Hifumi, Shinsuke Inagi, Ikuyoshi Tomita
Summary: Donor-acceptor type p-conjugated polymers with heterole units were synthesized by reacting a regioregular organometallic polymer containing both reactive titanacyclopentadiene and electron-donor thiophene-2,5-diyl units in the main chain with electrophiles. A polymer with an electron-accepting phosphole unit was obtained with a 54% yield and a number-average molecular weight (M(n)) of 3,000 and a molecular weight distribution (M(w)/M(n)) of 1.9. The obtained polymer showed a narrow band gap energy level (E(g)) of 1.78 eV due to the alternating structure of thiophene and phosphole.
DESIGNED MONOMERS AND POLYMERS
(2023)
Article
Chemistry, Multidisciplinary
Olesja Koleda, Tobias Prenzel, Johannes Winter, Tomoki Hirohata, Maria de Jesus Galvez-Vazquez, Dieter Schollmeyer, Shinsuke Inagi, Edgars Suna, Siegfried R. Waldvogel
Summary: Cathodic synthesis enables the sustainable access to 1-hydroxy- and 1-oxy-quinazolin-4-ones utilizing easily accessible nitro starting materials. This method features mild reaction conditions, inexpensive and reusable carbon-based electrode materials, an undivided electrochemical setup, and constant current conditions. The use of sulphuric acid as a supporting electrolyte and cyclization catalyst, along with the broad applicability demonstrated with 27 differently substituted derivatives achieving high yields (up to 92%), emphasizes its significance for preparative applications. Mechanistic studies based on cyclic voltammetry measurements reveal the selective reduction of nitro substrates to hydroxylamines as a crucial step.
Article
Chemistry, Multidisciplinary
Yaqian Zhou, Elena Villani, Tomoyuki Kurioka, Yanyun Zhang, Ikuyoshi Tomita, Shinsuke Inagi
Summary: In this study, an electrochemical strategy for precise control of the location of aggregation-induced emission (AIE) molecules on patterned electrodes is reported, resulting in photoluminescent and electrochemiluminescent patterns with a variety of colors. Combining the electrooxidation process with various conducting polymers (CPs) and bipolar electrochemistry, gradient luminescent patterns can be easily achieved. The findings suggest that this electrochemical method provides a way to develop abundant luminescent patterns.
Article
Polymer Science
Alvin Tanudjaja, Makoto Higuchi, Tomohiro Imai, Yoshimasa Matsumura, Ryoyu Hifumi, Shinsuke Inagi, Ikuyoshi Tomita
Summary: pi-Conjugated poly(arylene ethynylene)s containing both thiophene-2,5-diyl and fused metallacycles were synthesized and studied for their optoelectronic features. The polymers showed solubility in organic solvents, narrow optical band gaps, and bathochromic shift in the absorption spectra.
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.
