MDPI AG Acta Medica Okayama 2073-4344 15 2 2025 Palladium-Catalyzed Decarbonylative Nucleophilic Halogenation of Acid Anhydrides 191 EN Tian Tian Graduate School of Natural Science and Technology, Okayama University Shuhei Uei Department of Chemistry, Faculty of Science, Okayama University Weidan Yan Graduate School of Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science (RIIS), Okayama University In this study, we developed a palladium-catalyzed decarbonylative nucleophilic halogenation reaction using inexpensive and readily available acid anhydrides as substrates. This approach effectively circumvents the instability of acyl chlorides and the low reactivity of acyl fluorides. The Pd/Xantphos catalyst system exhibited excellent compatibility with the thermodynamically and kinetically challenging reductive elimination of C–X bonds (X = I, Br, and Cl) from Pd(II) intermediates. Notably, for electron-donating substrates, adopting an open system significantly improved the reaction efficiency. The positive effect of the open system may be due to the reversible nature of CO insertion and deinsertion, which helps direct the reaction toward the desired pathway by allowing the generated CO to exit the reaction system. Mechanistic studies suggest that the reaction proceeds through a highly reactive acyl halide intermediate, followed by a unimolecular fragment coupling (UFC) pathway via decarbonylation or an alternative pathway involving the formation of an activated anionic palladate complex in the presence of lithium halide. No potential conflict of interest relevant to this article was reported.

Royal Society of Chemistry (RSC) Acta Medica Okayama 1477-0520 2025 From Carboxylic Acids or Their Derivatives to Amines and Ethers: Modern Decarboxylative Approaches for Sustainable C–N and C–O Bond Formation EN Weidan Yan Graduate School of Natural Science and Technology, Okayama University Tian Tian Graduate School of Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science (RIIS), Okayama University Amines and ethers represent essential structural motifs in pharmaceuticals, natural products, organic materials, and catalytic systems. The development of novel, environmentally friendly, and cost-effective strategies for constructing C–N and C–O bonds is therefore of significant importance for the synthesis of these compounds. In recent years, carboxylic acids and their derivatives have emerged as attractive, inexpensive, non-toxic, and readily available synthetic building blocks, serving as promising alternatives to aryl halides. Growing evidence has demonstrated that decarboxylative amination and etherification of carboxylic acid derivatives offer a powerful approach for the synthesis of amines and ethers. These transformations proceed via three principal mechanistic pathways, each offering high atom economy. Specifically, carbanions (or organometallic species) generated through heterolytic decarboxylation can react with suitable electrophiles to form C–heteroatom bonds. In contrast, carbon-centred radicals produced through homolytic decarboxylation can couple with heteroatom-based reagents via radical recombination or oxidative trapping. Additionally, carbocations are typically formed via electrochemical oxidation of carboxylic acids: oxidative decarboxylation first yields a carbon radical, which is then further oxidized at the anode to generate a carbocation. This highly electrophilic intermediate can subsequently be intercepted by heteroatom nucleophiles to construct C–N or C–O bonds. This review highlights recent advances in the field, with a focus on transition metal catalysis, photoredox catalysis, and electrochemical methods for decarboxylative amination and etherification. No potential conflict of interest relevant to this article was reported.

Wiley Acta Medica Okayama 1861-4728 2025 Alkoxy‐Substituted Anthrabis(Thiadiazole)‐Terthiophene Copolymers for Organic Photovoltaics: A Unique Wavy Backbone Enhances Aggregation, Molecular Order, and Device Efficiency e00678 EN Yi Yan Graduate School of Environmental, Life, Natural Science and Technology, Okayama University Hiroki Mori Research Institute for Interdisciplinary Science, Okayama University Tomoki Yoshino Graduate School of Environmental, Life, Natural Science and Technology, Okayama University Ryuki Inami Graduate School of Environmental, Life, Natural Science and Technology, Okayama University Jiaxin Chang Graduate School of Environmental, Life, Natural Science and Technology, Okayama University Junqing Gao Graduate School of Environmental, Life, Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University Two polymer donors, PATz3T-o6BO and PATz3T-o6HD, incorporating alkoxy-substituted anthra[1,2-c:5,6-c′]bis([1,2,5]thiadiazole), were strategically designed and synthesized. The unique wavy backbone of these polymers effectively reduced aggregation, leading to enhanced solubility and significantly improved molecular ordering. Consequently, the PATz3T-o6HD:Y12-based solar cells achieved a power conversion efficiency (PCE) of 7.94%. These findings provide valuable insights into the molecular design of high-performance polymer donors for organic photovoltaics (OPVs). No potential conflict of interest relevant to this article was reported.

Georg Thieme Verlag KG Acta Medica Okayama 0039-7881 53 17 2021 Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C–F Bond Activation 3045 3050 EN Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University Jingwen You Graduate School of Natural Science and Technology, Okayama University Qiang Chen Graduate School of Natural Science and Technology, Okayama University Nickel-catalyzed decarbonylative thioetherification of acyl fluorides has been developed. This transformation allows an array of acyl fluorides to react with thiophenols. A wide range of functional groups are well tolerated and the corresponding sulfides can be obtained in good to excellent yields. This protocol provides the formation of diverse carbon–sulfur bonds via a highly efficient decarbonylative process. No potential conflict of interest relevant to this article was reported.

Royal Society of Chemistry (RSC) Acta Medica Okayama 1359-7345 57 30 2021 Palladium-catalyzed decarbonylative and decarboxylative cross-coupling of acyl chlorides with potassium perfluorobenzoates affording unsymmetrical biaryls 3696 3699 EN Liyan Fu Graduate School of Natural Science and Technology, Okayama University Jingwen You Graduate School of Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University This paper describes the synthesis of unsymmetrical biaryls by the palladium-catalyzed cross-coupling reaction of acyl chlorides with potassium perfluorobenzoates. This transformation is unique in that it involves simultaneous decarbonylation and decarboxylation under redox-neutral conditions. Compared to conventional cross-coupling protocols for the synthesis of unsymmetrical biaryls, the two reactants in this synthetic strategy can be readily prepared from abundant and inexpensive aromatic carboxylic acids. No potential conflict of interest relevant to this article was reported.

Thieme Gruppe Acta Medica Okayama 0936-5214 2020 Nickel-Catalyzed Decarbonylative Alkynylation of Acyl Fluorides with Terminal Alkynes under Copper-Free Conditions EN Qiang Chen Graduate School of Natural Science and Technology, Okayama University Liyan Fu Graduate School of Natural Science and Technology, Okayama University Jingwen You Graduate School of Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University Nickel-catalyzed decarbonylative alkynylation of acyl fluorides with terminal silylethynes under copper-free conditions is described. This newly developed method has a wide substrate scope, affording internal silylethynes in moderate to high yields. The formation of 1,3-diynes as homocoupled products and conjugate enones as carbonyl-retentive products were effectively suppressed. No potential conflict of interest relevant to this article was reported.

MDPI Acta Medica Okayama 1420-3049 25 17 2020 Synthesis and Physicochemical Properties of 2,7-Disubstituted Phenanthro[2,1-b:7,8-b']dithiophenes 3842 EN Zhenfei Ji Graduate School of Natural Science and Technology, Okayama University Zeliang Cheng Graduate School of Natural Science and Technology, Okayama University Hiroki Mori Research Institute for Interdisciplinary Science, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University We report the design, synthesis, and physicochemical properties of an array of phenanthro[2,1-b:7,8-b']dithiophene (PDT-2) derivatives by introducing five types of alkyl (CnH2n+1; n = 8, 10, 12, 13, and 14) or two types of decylthienyl groups at 2,7-positions of the PDT-2 core. Systematic investigation revealed that the alkyl length and the type of side chains have a great effect on the physicochemical properties. For alkylated PDT-2, the solubility was gradually decreased as the chain length was increased. For instance, C-8-PDT-2 exhibited the highest solubility (5.0 g/L) in chloroform. Additionally, substitution with 5-decylthienyl groups showed poor solubility in both chloroform and toluene, whereas PDT-2 with 4-decylthienyl groups resulted in higher solubility. Furthermore, UV-vis absorption of PDT-2 derivatives substituted by decylthienyl groups showed a redshift, indicating the extension of their pi-conjugation length. This work reveals that modification of the conjugated core by alkyl or decylthienyl side chains may be an efficient strategy by which to change the physicochemical properties, which might lead to the development of high-performance organic semiconductors. No potential conflict of interest relevant to this article was reported.

MDPI Acta Medica Okayama 1422-0067 21 7 2020 Synthesis of Dinaphtho[2,3-d:2',3'-d']anthra[1,2-b:5,6-b']dithiophene (DNADT) Derivatives: Effect of Alkyl Chains on Transistor Properties 2447 EN Takumi Ishida Graduate School of Natural Science and Technology, Okayama University Yuta Sawanaka Graduate School of Natural Science and Technology, Okayama University Ryota Toyama Graduate School of Natural Science and Technology, Okayama University Zhenfei Ji Graduate School of Natural Science and Technology, Okayama University Hiroki Mori Research Institute for Interdisciplinary Science, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University To investigate organic field-effect transistor (OFET) properties, a new thienoacene-type molecule, 4,14-dihexyldinaphtho[2,3-d:2',3'-d']anthra[1,2-b:5,6-b']dithiophene (C6-DNADT), consisting of pi-conjugated nine aromatic rings and two hexyl chains along the longitudinal molecular axis has been successfully synthesized by sequential reactions, including Negishi coupling, epoxidation, and cycloaromatization. The fabricated OFET using thin films of C6-DNADT exhibited p-channel FET properties with field-effect mobilities (mu) of up to 2.6 x 10(-2) cm(2) V-1 s(-1), which is ca. three times lower than that of the parent DNADT molecule (8.5 x 10(-2) cm(2) V-1 s(-1)). Although this result implies that the installation of relatively short alkyl chains into the DNADT core is not suitable for transistor application, the origins for the FET performance obtained in this work is fully discussed, based on theoretical calculations and solid-state structure of C6-DNADT by grazing incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) analyses. The results obtained in this study disclose the effect of alkyl chains introduced onto the molecule on transistor characteristics. No potential conflict of interest relevant to this article was reported.

American Chemical Society Acta Medica Okayama 15237060 22 6 2020 Palladium-Catalyzed Decarbonylative Alkylation of Acyl Fluorides 2350 2353 EN Liyan Fu Graduate School of Natural Science and Technology, Okayama University Qiang Chen Graduate School of Natural Science and Technology, Okayama University Zhenhua Wang Graduate School of Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University Palladium-catalyzed decarbonylative alkylation reactions of acyl fluorides have been developed using alkylboranes having β-hydrogens. A wide range of functional groups were well tolerated, even at the high temperature required for decarbonylation. This protocol provides a diverse C(sp2)–C(sp3) bond formation via a highly efficient decarbonylative process. The hemilabile bidentate ligand DPPE plays a crucial role for retardation of the undesired β-hydride elimination. No potential conflict of interest relevant to this article was reported.

American Chemical Society Acta Medica Okayama 0022-3263 84 23 2019 Copper-Catalyzed Regioselective Aminothiolation of Aromatic and Aliphatic Alkenes with N-Fluorobenzenesulfonimide and Thiols through Three-Component Radical Coupling 15373 15379 EN Masayuki Iwasaki Research Institute for Interdisciplinary Science, Okayama University Kosei Nonaka Graduate School of Natural Science and Technology, Okayama University Song Zou Yuta Sawanaka Graduate School of Natural Science and Technology, Okayama University Takaaki Shinozaki Graduate School of Natural Science and Technology, Okayama University Tomoya Fujii Graduate School of Natural Science and Technology, Okayama University Kiyohiko Nakajima Graduate School of Natural Science and Technology, Okayama University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University Copper-catalyzed regioselective aminothiolation of terminal and internal alkenes with N-fluorobenzenesulfonimide and thiols has been developed. The three-component reaction is promoted by the addition of dimethyl sulfide. In addition to aromatic alkenes, aliphatic alkenes are subjected to the reaction, affording various aminothiolation adducts as single regioisomers. The radical process is proposed by preliminary mechanistic studies, involving radical trap and radical clock experiments. No potential conflict of interest relevant to this article was reported.

Chemical Society of Japan Acta Medica Okayama 03667022 48 3 2019 Copper-catalyzed Regioselective Chloroamination of Alkenes with Chlorotrimethylsilane and N-Fluorobenzenesulfonimide under Microwave-assisted Conditions 281 283 EN Masayuki Iwasaki Research Institute for Interdisciplinary Science, Okayama University Jie Xu Graduate School of Natural Science and Technology, Okayama University Yukari Tani Graduate School of Natural Science and Technology, Okayama University Liyan Fu Graduate School of Natural Science and Technology, Okayama University Yuichi Ikemoto Graduate School of Natural Science and Technology, Okayama University Yasuyuki Ura Department of Chemistry, Biology, and Environmental Science, Faculty of Science, Nara Women’s University Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University A copper-catalyzed chloroamination of alkenes with chlorotrimethylsilane and N-fluorobenzenesulfonimide has been developed. The reactions were complete within 1 h at 120 degrees C by means of microwave heating. The present chloroamination proceeds with a perfect regioselectivity and is compatible with various functional groups. The preliminary mechanistic investigation revealed that the reaction involves a radical process. The utility of the present method was demonstrated by scalable, operationally simple and safe system. No potential conflict of interest relevant to this article was reported.

American Chemical Society Acta Medica Okayama 1523-7060 18 7 2016 Palladium-Catalyzed Regio- and Stereoselective Carbothiolation of Terminal Alkynes with Azolyl Sulfides 1642 1645 EN Masayuki Iwasaki Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Nikola Topolovčan Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Hao Hu Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Yugo Nishimura Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Glwadys Gagnot Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Rungsaeng Na nakorn Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Ramida Yuvacharaskul Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Kiyohiko Nakajima Department of Chemistry, Aichi University of Education Yasushi Nishihara Division of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama University Palladium-catalyzed carbothiolation of terminal alkynes with azolyl sulfides affords various 2-(azolyl)alkenyl sulfides with perfect regio- and stereoselectivities. The present addition reaction proceeded through a direct cleavage of carbon-sulfur bonds in azolyl sulfides. The resulting adducts that are useful intermediates in organic synthesis are further transformed to multisubstituted olefins containing azolyl moieties. No potential conflict of interest relevant to this article was reported.

American Chemical Society Acta Medica Okayama 1523-7060 19 5 2017 Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed Dehydrogenative Direct Selenation of C(sp2)-H Bonds with Elemental Selenium in Air 1092 1095 EN Masayuki Iwasaki Research Institute for Interdisciplinary Science, Okayama University Natsumi Miki Graduate School of Natural Science and Technology, Okayama University Yuta Tsuchiya Graduate School of Natural Science and Technology, Okayama University Kiyohiko Nakajima Department of Chemistry, Aichi University of Education Yasushi Nishihara Research Institute for Interdisciplinary Science, Okayama University Nickel-catalyzed direct selenation of benzamides bearing an 8-quinolyl auxiliary with elemental selenium provides benzoisoselenazolones in good yield via carbon-selenium and nitrogen-selenium bond formation under aerobic conditions. In addition to aryl C-H bonds, the method can also be applied to alkenyl C-H bonds, constructing an isoselenazolone skeleton. Simple mechanistic analysis shows that the reaction proceeds through a rate-determining C-H bond cleavage. The obtained benzoisoselenazolones are transformed into various organoselenium compounds and utilized as the catalyst for bromolactonization of alkenoic acids. No potential conflict of interest relevant to this article was reported.

Elsevier Science BV. Acta Medica Okayama 0926-3373 102 3-4 2011 Improvement in sulfur desorption of NOX storage and reduction catalysts using a Ba–Ti composite oxide 620 626 EN Toshiyuki Tanaka Ichirou Tajima Yuichi Kato Yasushi Nishihara Hirofumi Shinjoh A Ba-Ti composite oxide was formed on a NOx storage and reduction catalyst via impregnation of a Ba-Ti precursor solution composed of H(2)O(2) added to a complex prepared using the citric acid method. The structure of the Ba-Ti composite in solution was analyzed by chemical composition analysis and FT-Raman and UV-vis spectroscopy. MM2 calculations were performed to propose its chemical structure. Both Ba and Ti together were found to form a composite molecule in the solution. Furthermore, TEM-EDX and XRD analyses of the Ba-Ti composite oxide on the catalyst prepared by impregnation with the Ba-Ti composite aqueous solution revealed that Ba and Ti in the catalyst were highly dispersed at the nm scale. The formation of the Ba-Ti composite oxide on the NSR catalyst enhanced sulfur desorption efficiency and led to high-performance NO(X) conversion as a NO(X) storage and reduction activity catalyst after desulfation treatment. It was assumed that the existence of nano-scaled Ba compounds combined with Ti was efficient for the inhibition of the sintering of barium sulfate and its facile decomposition. It was found that dispersion of Ba compounds for NO(X) storage materials using a Ba-Ti complex solution is an efficient way to improve the durability of NSR catalysts. No potential conflict of interest relevant to this article was reported.

Pergamon-Elsevier Science Ltd. Acta Medica Okayama 0040-4039 51 2 2010 Palladium- and base-free synthesis of conjugated ynones by cross-coupling reactions of alkynylboronates with acid chlorides mediated by CuCl 306 308 EN Yasushi Nishihara Daisuke Saito Eiji Inoue Yoshiaki Okada Mikihiro Miyazaki Yoshiaki Inoue Kentaro Takagi Alkynylboronates can be employed as a practical and versatile precursor for a variety of pi-conjugated organic compounds. In the presence of Cu(I) salt, cross-coupling reactions of acid chlorides with alkynylboronates giving rise to the corresponding conjugated ynones takes place readily in aprotic polar solvents such as DMI under neutral conditions. No potential conflict of interest relevant to this article was reported.