Georg Thieme Verlag KGActa Medica Okayama0039-788153172021Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C–F Bond Activation30453050ENYasushiNishiharaResearch Institute for Interdisciplinary Science, Okayama UniversityJingwenYouGraduate School of Natural Science and Technology, Okayama UniversityQiangChenGraduate School of Natural Science and Technology, Okayama UniversityNickel-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 Okayama1359-734557302021Palladium-catalyzed decarbonylative and decarboxylative cross-coupling of acyl chlorides with potassium perfluorobenzoates affording unsymmetrical biaryls36963699ENLiyanFuGraduate School of Natural Science and Technology, Okayama UniversityJingwenYouGraduate School of Natural Science and Technology, Okayama UniversityYasushiNishiharaResearch Institute for Interdisciplinary Science, Okayama UniversityThis 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 GruppeActa Medica Okayama0936-52142020Nickel-Catalyzed Decarbonylative Alkynylation of Acyl Fluorides with Terminal Alkynes under Copper-Free ConditionsENQiangChenGraduate School of Natural Science and Technology, Okayama UniversityLiyanFuGraduate School of Natural Science and Technology, Okayama UniversityJingwenYouGraduate School of Natural Science and Technology, Okayama UniversityYasushiNishiharaResearch Institute for Interdisciplinary Science, Okayama UniversityNickel-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.MDPIActa Medica Okayama1420-304925172020Synthesis and Physicochemical Properties of 2,7-Disubstituted Phenanthro[2,1-b:7,8-b']dithiophenes3842ENZhenfeiJiGraduate School of Natural Science and Technology, Okayama UniversityZeliangChengGraduate School of Natural Science and Technology, Okayama UniversityHirokiMoriResearch Institute for Interdisciplinary Science, Okayama UniversityYasushiNishiharaResearch Institute for Interdisciplinary Science, Okayama UniversityWe 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.MDPIActa Medica Okayama1422-00672172020Synthesis of Dinaphtho[2,3-d:2',3'-d']anthra[1,2-b:5,6-b']dithiophene (DNADT) Derivatives: Effect of Alkyl Chains on Transistor Properties2447ENTakumiIshidaGraduate School of Natural Science and Technology, Okayama UniversityYutaSawanakaGraduate School of Natural Science and Technology, Okayama UniversityRyotaToyamaGraduate School of Natural Science and Technology, Okayama UniversityZhenfeiJiGraduate School of Natural Science and Technology, Okayama UniversityHirokiMoriResearch Institute for Interdisciplinary Science, Okayama UniversityYasushiNishiharaResearch Institute for Interdisciplinary Science, Okayama UniversityTo 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 SocietyActa Medica Okayama152370602262020Palladium-Catalyzed Decarbonylative Alkylation of Acyl Fluorides23502353ENLiyanFuGraduate School of Natural Science and Technology, Okayama UniversityQiangChenGraduate School of Natural Science and Technology, Okayama UniversityZhenhuaWangGraduate School of Natural Science and Technology, Okayama UniversityYasushiNishiharaResearch Institute for Interdisciplinary Science, Okayama UniversityPalladium-catalyzed decarbonylative alkylation reactions of acyl fluorides have been developed using alkylboranes having -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 -hydride elimination.No potential conflict of interest relevant to this article was reported.American Chemical SocietyActa Medica Okayama 0022-326384232019Copper-Catalyzed Regioselective Aminothiolation of Aromatic and Aliphatic Alkenes with N-Fluorobenzenesulfonimide and Thiols through Three-Component Radical Coupling1537315379ENMasayukiIwasakiResearch Institute for Interdisciplinary Science, Okayama UniversityKoseiNonakaGraduate School of Natural Science and Technology, Okayama UniversitySongZouYutaSawanakaGraduate School of Natural Science and Technology, Okayama UniversityTakaakiShinozakiGraduate School of Natural Science and Technology, Okayama UniversityTomoyaFujiiGraduate School of Natural Science and Technology, Okayama UniversityKiyohikoNakajimaGraduate School of Natural Science and Technology, Okayama UniversityYasushiNishiharaResearch 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 JapanActa Medica Okayama036670224832019 Copper-catalyzed Regioselective Chloroamination of Alkenes with Chlorotrimethylsilane and N-Fluorobenzenesulfonimide under Microwave-assisted Conditions281283ENMasayukiIwasakiResearch Institute for Interdisciplinary Science, Okayama UniversityJieXuGraduate School of Natural Science and Technology, Okayama UniversityYukariTaniGraduate School of Natural Science and Technology, Okayama UniversityLiyanFuGraduate School of Natural Science and Technology, Okayama UniversityYuichiIkemotoGraduate School of Natural Science and Technology, Okayama UniversityYasuyukiUraDepartment of Chemistry, Biology, and Environmental Science, Faculty of Science, Nara Womenfs UniversityYasushiNishiharaResearch 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 SocietyActa Medica Okayama1523-70601872016Palladium-Catalyzed Regio- and Stereoselective Carbothiolation of Terminal Alkynes with Azolyl Sulfides16421645ENMasayukiIwasakiDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityNikolaTopolovčanDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityHaoHuDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityYugoNishimuraDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityGlwadysGagnotDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityRungsaeng NanakornDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityRamidaYuvacharaskulDivision of Earth, Life, and Molecular Sciences, Graduate School of Natural Science and Technology, Okayama UniversityKiyohikoNakajimaDepartment of Chemistry, Aichi University of EducationYasushiNishiharaDivision 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 SocietyActa Medica Okayama1523-70601952017Synthesis of Benzoisoselenazolone Derivatives by Nickel-Catalyzed Dehydrogenative Direct Selenation of C(sp2)-H Bonds with Elemental Selenium in Air10921095ENMasayukiIwasaki Research Institute for Interdisciplinary Science, Okayama UniversityNatsumiMikiGraduate School of Natural Science and Technology, Okayama UniversityYutaTsuchiyaGraduate School of Natural Science and Technology, Okayama UniversityKiyohikoNakajimaDepartment of Chemistry, Aichi University of EducationYasushiNishihara 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 Okayama0926-33731023-42011Improvement in sulfur desorption of NOX storage and reduction catalysts using a Ba–Ti composite oxide620626ENToshiyukiTanakaIchirouTajimaYuichiKatoYasushiNishiharaHirofumiShinjohA 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 Okayama0040-40395122010Palladium- and base-free synthesis of conjugated ynones by cross-coupling reactions of alkynylboronates with acid chlorides mediated by CuCl306308ENYasushiNishiharaDaisukeSaitoEijiInoueYoshiakiOkadaMikihiroMiyazakiYoshiakiInoueKentaroTakagiAlkynylboronates 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.