2022/11/25 更新

写真b

ミノウラ マオ
箕浦 真生
MINOURA Mao
*大学が定期的に情報更新している項目(その他は、researchmapの登録情報を転載)
所属*
理学部 化学科
理学研究科 化学専攻 博士課程後期課程
理学研究科 化学専攻 博士課程前期課程
職名*
教授
学位
博士(理学) ( 東京大学 )
連絡先
メールアドレス
研究テーマ*
  • 有機元素化学・物理有機化学。周期表上の様々な元素の特性を引き出すことを目的とし、新規有機元素化合物の合成と構造・反応・物性に関する実験的および理論的研究に取り組む。これまでに未知である化学結合の性質解明による学術的再生産や元素の性質を活かした機能性分子創製、新反応の開発をめざしている。

  • 研究キーワード
  • 有機元素化学

  • 有機金属化学

  • 環境化学

  • 有機化学

  • 物理有機化学

  • 結晶学

  • 学内職務経歴*
    • 2013年4月 - 現在 
      理学部   化学科   教授
    • 2013年4月 - 現在 
      理学研究科   化学専攻 博士課程前期課程   教授
    • 2013年4月 - 現在 
      理学研究科   化学専攻 博士課程後期課程   教授
     

    研究分野

    • ナノテク・材料 / グリーンサステイナブルケミストリー、環境化学  / 環境化学

    • ライフサイエンス / 生物有機化学  / 有機元素化学

    • ナノテク・材料 / 構造有機化学、物理有機化学  / 有機元素化学

    経歴

    • 2013年4月 - 現在 
      立教大学   理学研究科 化学専攻博士課程後期課程   教授

      詳細を見る

    • 2013年4月 - 現在 
      立教大学   理学研究科 化学専攻博士課程前期課程   教授

      詳細を見る

    • 2013年4月 - 現在 
      立教大学   理学部 化学科   教授

      詳細を見る

    • 2008年4月 - 2013年3月 
      北里大学理学部   准教授

      詳細を見る

    • 2008年4月 - 2009年3月 
      京都大学化学研究所   客員准教授

      詳細を見る

    • 1999年9月 - 2008年3月 
      北里大学理学部   講師

      詳細を見る

    • 2003年9月 - 2004年8月 
      米国コロンビア大学化学科   客員研究員

      詳細を見る

    • 1995年4月 - 1999年8月 
      広島大学理学部   助手

      詳細を見る

    ▼全件表示

    学歴

    • - 1995年3月 
      東京大学   理学系研究科   化学専攻

      詳細を見る

      国名: 日本国

      researchmap

    • - 1990年9月 
      埼玉大学   理学研究科   化学専攻

      詳細を見る

      国名: 日本国

      researchmap

    • 1984年4月 - 1988年3月 
      埼玉大学   理学部   化学科

      詳細を見る

      国名: 日本国

      researchmap

    論文

    • Synthesis and Optical Properties of 1,2,5,10-Tetraphenylanthra[2,3-b]phosphole Derivatives 査読有り 国際誌

      Yuta Kudoh, Kaori Fujii, Yoshifumi Kimura, Mao Minoura, Yoshihiro Matano

      The Journal of Organic Chemistry87 ( 15 ) 10493 - 10500   2022年8月5日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:American Chemical Society ({ACS})  

      1,2,5,10-Tetraphenylanthra[2,3-b]phosphole oxides and 1-methyl-1,2,5,10-tetraphenylanthra[2,3-b]phospholium salts were prepared, and their optical properties were investigated. The substituent at the para position and the fused anthracene moiety were found to exert significant impacts on the fluorescence properties of the P-bridged 2-styrylanthracene skeleton.

      DOI: 10.1021/acs.joc.2c01107

      Scopus

      PubMed

      researchmap

    • 9‐(Diphenylphosphoryl)‐10‐(phenylethynyl)anthracene Derivatives: Synthesis and Implications for the Substituent and Solvent Effects on the Light‐Emitting Properties 査読有り

      Nina Murayama, Joel Hao Jorolan, Mao Minoura, Haruyuki Nakano, Tadaaki Ikoma, Yoshihiro Matano

      ChemPhotoChem   2022年6月13日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Herein, we report a series of 9-(diphenylphosphoryl)-10-(phenylethynyl)anthracenes (DPPPEAs) as novel fluorescent 9,10-disubstituted anthracene derivatives. The DPPPEAs were prepared by Sonogashira coupling of (10-bromoanthracen-9-yl)diphenylphosphine oxide with terminal arylacetylenes, and their structures were fully characterized. UV/Vis fluorescence spectroscopy and theoretical calculations were used to evaluate substituent effects on fluorescence properties of DPPPEAs. The nature of emissive excited state of DPPPEAs was found to vary greatly depending on the substituent, solvent, and temperature. Unsubstituted DPPPEA emitted intense fluorescence from locally excited (LE) state, whereas donor-acceptor (D-A) type DPPPEAs substituted with diphenylamino groups showed strong solvatofluorochromism derived from the charge-transfer (CT) state. Notably, carbazolyl derivatives exhibited fluorescence from LE hybridized with CT state. The disappearance of CT emission in rigid media suggests that solvent reorganization plays a crucial role in producing large Stokes shifts of D-A type derivatives. The DPPPEAs have also been found to function as annihilators in porphyrin-sensitized triplet–triplet annihilation processes.

      DOI: 10.1002/cptc.202200100

      Scopus

      researchmap

    • Stereoselective Transesterification of P ‐Chirogenic Hydroxybinaphthyl Phosphinates 査読有り 国際誌

      Akari Kawajiri, Taro Udagawa, Mao Minoura, Toshiaki Murai

      ChemistryOpen   e202100294   2022年3月8日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      The substitution reaction of phosphinates with a binaphthyloxy group at the phosphorus atom with lithium alkoxides proceeded with good to high efficiencies to give P-chirogenic phosphinates with a high enantiomeric ratio. As alcohols, primary, secondary, and tertiary alcohols could be used, and the use of tert-butyl alcohol yielded the products with a higher enantiomeric ratio. A substrate with two different alkyl groups on the phosphorus atom could also participate in the substitution reaction to give the corresponding products in good yields with excellent selectivity. The molecular structures of one of the substrates and the corresponding products, determined by X-ray analyses, proved that the substitution reaction at the phosphorus atom proceeded with inversion of the absolute configuration. The usefulness of the reaction was demonstrated by using it to prepare a drug candidate for Duchenne muscular dystrophy. Finally, thionation of the resulting phosphinates was carried out to form P-chirogenic phosphinothioates.

      DOI: 10.1002/open.202100294

      Scopus

      PubMed

      researchmap

    • Copper(II) Complexes of 10,20-Diaryl-5,15-diazaporphyrin: Alternative Synthesis, Excited State Dynamics, and Substituent Effect on the <sup>1</sup>O<inf>2</inf>-Generation Efficiency 査読有り

      Hikari Ochiai, Tomoaki Miura, Tadaaki Ikoma, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      Bulletin of the Chemical Society of Japan95 ( 3 ) 427 - 432   2022年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The synthesis, excited state dynamics, and substituent effect on the 1O2-generation efficiency of several copper(II) complexes of 5,15-diazaporphyrin (CuDAPs) bearing peripheral substituents are reported. 10,20-Diaryl-CuDAPs were prepared via a new method consisting of metal-templated cyclization and N-dealkylation as key steps. The effect of the β-substituents on the optical and redox properties of CuDAP was stronger than that of the meso-aryl groups, which can be explained by considering the characteristics of the HOMO and LUMO of the DAP ring. The excited state dynamics and 1O2-generation efficiency of CuDAPs were studied using time-resolved spectroscopic techniques; the electronic effect of the meso-aryl groups on the triplet lifetime and 1O2-generation quantum yield was relatively weak, whereas that of the β-(1-pyrazolyl) groups was appreciable. The analysis of the temperature dependence of phosphorescence spectra of 10,20-bis(2,4,6-trimethylphenyl)-CuDAP allowed the energy gap between the excited trip-quartet and trip-doublet states to be determined. The relatively long triplet lifetimes of CuDAPs show their potential for future application as photosensitizers.

      DOI: 10.1246/bcsj.20220002

      Scopus

      researchmap

    • Primary Phosphines and Phosphine Oxides with a Stereogenic Carbon Center Adjacent to the Phosphorus Atom: Synthesis and Anti-Markovnikov Radical Addition to Alkenes 査読有り

      Toshiaki Murai, Ryota Wada, Kouji Iwata, Yuuki Maekawa, Kazuma Kuwabara, Mao Minoura

      Organics   2021年11月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.3390/org2040023

      researchmap

    • Synthesis, Optical Properties, and Electrochemical Behavior of 5,10,15,20-Tetraaryl-5,15-diazaporphyrin-Amine Hybrids 査読有り 国際誌

      Yuna Satoh, Yutaro Fujita, Naoya Muramatsu, Ko Furukawa, Tadaaki Ikoma, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      ChemPlusChem86 ( 10 ) 1476 - 1486   2021年10月

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      This work reports a series of covalently linked hybrids comprising 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (M-TADAP; M = Ni, Zn, Cu) and amines. M-TADAP-amine hybrids were prepared via the metal-templated cyclization of the corresponding metal(II)-dipyrrin complexes and redox reactions on the DAP unit. In the UV/vis/near-IR absorption spectra of the hybrids containing an 18π-electron DAP ring, broad charge-transfer bands were observed, reflecting the electron-donating property of the para-aminophenyl groups and the electron-accepting property of the 18π TADAP dication. The electrochemical behavior of the M-TADAP-amine hybrids was strongly dependent on the structure of the peripheral amine units. Further electrochemical oxidation of the hybrids bearing N-Ph groups conceivably generated amine-centered radicals, which sequentially underwent irreversible coupling to form benzidine-linked M-TADAP polymer films. The Ni-TADAP-benzidine polymer exhibited the electric conductivity of 2×10−3 S m−1.

      DOI: 10.1002/cplu.202100429

      Scopus

      PubMed

      researchmap

    • Gas Adsorption in R 2 ‐MOF‐5 Difunctionalized with Alkyl Groups 査読有り

      Koh Sugamata, Sho Kobayashi, Teruyuki Iihama, Mao Minoura

      European Journal of Inorganic Chemistry2021 ( 31 ) 3185 - 3190   2021年8月20日

      詳細を見る

      掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      Zinc terephthalate metal−organic framework (MOF) MOF-5 and some of its dialkylated derivatives (R2-MOF-5; R=Me, Et, Pr, Bu) were obtained from a solvothermal synthesis using 2,5-dialkyl-1,4-benzenedicarboxylic acids with zinc nitrite. The effect of the solvent on the solvothermal synthesis of R2-MOF-5 was investigated. For R=H and Me, interpenetrating or non-interpenetrating MOFs obtained depending on the choice of reaction solvent, while for R=Et, Pr, and Bu, no such solvent effect was observed, and only jungle-gym-type MOFs were generated. All compounds were fully characterized using powder X-ray diffraction analysis (PXRD), Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). After activation, all these compounds exhibit significant porosity, as confirmed by N2-, H2-, and CO2-sorption experiments. The N2-adsorption capacity of these compounds depends on the size of the attached alkyl groups, while the H2-uptake values tend to increase for the alkyl-functionalized MOFs relative to the unfunctionalized parent MOFs and exhibit a maximum value for Pr2-MOF-5.

      DOI: 10.1002/ejic.202100466

      Scopus

      researchmap

    • Synthesis of Dialkyl-Diphosphenes and -Distibenes that Bear Extended Triptycyl Groups 査読有り

      Ryohei Nishino, Mao Minoura

      Bulletin of the Chemical Society of Japan94 ( 12 ) 2919 - 2921   2021年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Dialkyl-diphosphenes and -distibenes of the type RTrp*2E2 (E = P, Sb; R = H, n-Pr) were synthesized and isolated using the steric protection of extended triptycyl groups (Trp*). The solubility of these diphosphenes and distibenes can be increased by installing a propyl group onto the bridgehead position of the triptycyl core (n-PrTrp*).

      DOI: 10.1246/bcsj.20210350

      Scopus

      researchmap

    • Broadened bioactivity and enhanced durability of two structurally distinct metal–organic frameworks containing Zn2+ ions and thiabendazole 査読有り 国際誌

      Daiya Kobayashi, Akira Hamakawa, Yuki Yamaguchi, Toshiaki Takahashi, Mitsuhiro Yanagita, Shigebumi Arai, Mao Minoura

      Dalton Transactions50 ( 21 ) 7176 - 7180   2021年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Royal Society of Chemistry ({RSC})  

      Novel metal-organic frameworks (MOFs) based on thiabendazole (TBZ) were developed. The two structurally distinct TBZ-MOFs synthesized in this study exhibited enhanced durability and a broader biocidal spectrum than either individual bioactive species (i.e., Zn2+ and TBZ). The characteristics of each TBZ-MOF are related to the coordination modes among the Zn2+ ions and ligand donors. The difference in water solubility between the two TBZ-MOFs due to the structural design allows for the controlled release of the desired bioactive component.

      DOI: 10.1039/D1DT00733E

      Scopus

      PubMed

      researchmap

    • Chemoselective and Stereoselective Alcoholysis of Binaphthyl Phosphonothioates: Straightforward Access to Both Stereoisomers of Biologically Relevant P-Stereogenic Phosphonothioates 査読有り 国際誌

      Kazuma Kuwabara, Yuuki Maekawa, Mao Minoura, Toshifumi Maruyama, Toshiaki Murai

      The Journal of Organic Chemistry85 ( 22 ) 14446 - 14455   2020年11月20日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:American Chemical Society (ACS)  

      P-Stereogenic phosphonothioates have attracted great attention due to their potent biological activities as analogues of phosphoric acids and phosphorothioates. We demonstrate here straightforward access to P-stereogenic phosphonothioates through the use of binaphthyl phosphonothioates as a chiral template. The first-step alcoholysis of binaphthyl phosphonothioates proceeded via a transfer of the axial chirality of a binaphthyl group to the central chirality of a phosphorus atom to give only monoalcohol adducts with moderate to excellent diastereoselectivities. Further alcoholysis of the obtained products in the presence of a small excess of alcohol and base proceeded with complete elimination of a binaphthyl group to give the corresponding P-stereogenic phosphonothioates with high enantiomeric excess. A DFT study of the reaction mechanisms in first-step alcoholysis indicated that the coordination of a sulfur atom to a sodium cation is the key factor in controlling the diastereoselectivities. This method can be applied to prepare both stereoisomers of a G6P analogue with high diastereomeric purity.

      DOI: 10.1021/acs.joc.0c00687

      Scopus

      PubMed

      researchmap

    • Structural analysis of interpenetrated methyl-modified MOF-5 and its gas-adsorption properties. 査読有り 国際誌

      Koh Sugamata, Daichi Yanagisawa, Keiko Awano, Teruyuki Iihama, Mao Minoura

      Acta crystallographica. Section C, Structural chemistry76 ( Pt 9 ) 845 - 849   2020年9月1日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      The first example of an interpenetrated methyl-modified MOF-5 with the formula Zn4O(DMBDC)3(DMF)2, where DMBDC2- is 2,5-dimethylbenzene-1,4-dicarboxylate and DMF is N,N-dimethylformamide (henceforth denoted as Me2MOF-5-int), namely, poly[tris(μ4-2,5-dimethylbenzene-1,4-dicarboxylato)bis(N,N-dimethylformamide)-μ4-oxido-tetrazinc(II)], [Zn4(C10H8O4)3O(C3H7NO)2]n, has been obtained from a solvothermal synthesis of 2,5-dimethylbenzene-1,4-dicarboxylic acid and Zn(NO3)2·6H2O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase-pure Me2MOF-5-int, which was thoroughly characterized by single-crystal and powder X-ray diffraction (PXRD), as well as by gas-adsorption analyses. The Brunauer-Emmett-Teller surface area of Me2MOF-5-int (660 m2 g-1), determined by N2 adsorption, is much lower than that of nonpenetrated Me2MOF-5 (2420 m2 g-1). However, Me2MOF-5-int displays an H2 uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is comparable to that of non-interpenetrated Me2MOF-5 (1.51 wt%).

      DOI: 10.1107/S2053229620010177

      Scopus

      PubMed

      researchmap

    • Structural analysis of and selective CO<inf>2</inf>adsorption in mixed-ligand hydroxamate-based metal-organic frameworks 査読有り 国際誌

      Koh Sugamata, Chikaze Takagi, Keiko Awano, Teruyuki Iihama, Mao Minoura

      Dalton Transactions49 ( 29 ) 9948 - 9952   2020年8月7日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Royal Society of Chemistry ({RSC})  

      Two mixed-ligand metal-organic frameworks, [Zn2(BDHA)0.5(INA)3] (MOF-1: H2BDHA = benzene-1,4-dihydroxamic acid; HINA = isonicotinic acid) and [Co2(BDHA)0.5(INA)3(DMF)] (MOF-2), were solvothermally synthesized and fully characterized by single-crystal X-ray crystallography as well as N2, H2, and CO2 gas-sorption measurements. The results constitute the first detailed analysis of the bonding environment around the hydroxamates in such MOFs, which are simultaneously decorated with Lewis-basic sites from the hydroxamate moieties and metal sites predisposed for coordinative unsaturation. MOF-2 shows a desirably selective adsorption of CO2 relative to N2.

      DOI: 10.1039/d0dt01105c

      Scopus

      PubMed

      researchmap

    • N,N-Diarylthiazol-5-amines: Structure-Specific Mechanofluorochromism and White Light Emission in the Solid State 査読有り

      Yuki Tsuchiya, Kirara Yamaguchi, Yohei Miwa, Shoichi Kutsumizu, Mao Minoura, Toshiaki Murai

      Bulletin of the Chemical Society of Japan93 ( 7 ) 927 - 935   2020年7月15日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1246/bcsj.20200083

      Scopus

      researchmap

    • (Thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes from the reaction of bis(methylene)-λ<sup>4</sup>-sulfane and bis(methylene)-λ<sup>4</sup>-selane with chloro(dimethylsulfide)gold(i) 査読有り 国際誌

      Koh Sugamata, Yukiko Urao, Mao Minoura

      Dalton Transactions49 ( 23 ) 7688 - 7691   2020年6月21日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Royal Society of Chemistry ({RSC})  

      The dinuclear (thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes1and2were obtained from the reaction of two equivalents of AuCl(SMe2) with the stable bis(methylene)-λ4-chalcogenanes3and4, respectively. The reaction proceeds under elimination of the chlorosilane moiety of3and4. Complexes1and2were characterized by spectroscopic and X-ray diffraction (XRD) analyses. The13C NMR signals for the carbene centers of 1 (309 ppm) and 2 (345 ppm) are by more than 150 ppm downfield shifted relative to those for other known (NHC)AuCl complexes. These results indicate that (chalcogeno)(silyl)carbenes, like (amino)(silyl)carbenes, belong to the push-spectator family of carbenes.

      DOI: 10.1039/d0dt00967a

      Scopus

      PubMed

      researchmap

    • Synthesis, structure, and reactivity of a thermally stable dialkylgermylene 査読有り

      Fumiaki Suzuki, Ryohei Nishino, Mariko Yukimoto, Koh Sugamata, Mao Minoura

      Bulletin of the Chemical Society of Japan93 ( 2 ) 249 - 251   2020年2月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The dialkylgermylene Trp*2Ge: (Trp*: peripherally extended sterically demanding alkyl groups based on the triptycyl (Trp) framework), was obtained from the reaction of Trp*Li with GeCl2¢ dioxane. The structure of Trp*2Ge: was unequivocally determined by NMR and UV-vis spectroscopy, mass spectrometry, and a single-crystal X-ray diffraction analysis. Moreover, the reactivity of Trp*2Ge: was examined.

      DOI: 10.1246/BCSJ.20190338

      Scopus

      researchmap

    • Naphthalene diimide-incorporated helical thienoacene: a helical molecule with high electron mobility, good solubility, and thermally stable solid phase 査読有り 国際誌

      Nobuhiko Ohtsuka, Masahiro Nakano, Sae Nakagawa, Md. Shahiduzzaman, Makoto Karakawa, Tetsuya Taima, Mao Minoura

      Chemical Communications56 ( 82 ) 12343 - 12346   2020年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Royal Society of Chemistry ({RSC})  

      A Naphthalene diimide (NDI)-incorporated helical thienoacene was developed. The compound has high electron mobility (1.4 cm2 V-1 s-1) thanks to its two-dimensional π-π interaction assisted by the intermolecular C-HO hydrogen bonding of the NDI moieties. Moreover, its bow-shaped π-skeleton reduces molecular fluctuation and gives the compound a thermally stable solid phase, which enables us to fabricate thermally stable organic devices.

      DOI: 10.1039/D0CC04634E

      Scopus

      PubMed

      researchmap

    • 2‐(2‐Hydroxyphenyl)‐5‐aminothiazoles: Synthesis and Properties Involving Dual Emissions 査読有り

      Toshiaki Murai, Mari Yoshihara, Kirara Yamaguchi, Mao Minoura

      Asian Journal of Organic Chemistry8 ( 7 ) 1102 - 1106   2019年7月

      詳細を見る

      掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      2-(2-Hydroxyphenyl)-5-aminothiazoles were prepared by two different methods to elucidate their photophysical properties. The first synthetic method involved the addition of thioamide dianions derived from secondary thioamides and nBuLi to thioforamides. Alternatively, Pd-catalyzed sequential addition of aromatic groups and diarylamines to commercially available thiazoles led to the precursors of the desired thiazoles. The molecular structures of the resulting thiazoles were determined by X-ray analyses. The thiazoles showed dual-emission in cyclohexane and in the solid state.

      DOI: 10.1002/ajoc.201900194

      Scopus

      researchmap

      その他リンク: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/ajoc.201900194

    • Synthesis of Redox-Switchable 5,15-Dialkyl-10,20-diaryl-5,15-diazaporphyrins and Diversification of Their N-Alkyl Groups 査読有り

      Asian J. Org. Chem8 ( 3 ) 352 - 355   2019年3月

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      DOI: 10.1002/ajoc.201900085

      Scopus

      researchmap

    • Systematic synthesis and crystal structures of tetraaryltellurium compounds Ar<inf>4</inf>Te<sup>IV</sup> 査読有り

      Sho Kobayashi, Koh Sugamata, Mao Minoura

      Bulletin of the Chemical Society of Japan92 ( 3 ) 661 - 663   2019年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Hypervalent tetraaryltellurium(IV) compounds of the type Ar4TeIV(1: Ar = C6H5; 2: Ar = p-H3CC6H4; 3: Ar = p-t-BuC6H4; 4: Ar = p-F3CC6H4) were prepared via a convenient one-pot reaction between the isolated corresponding ArLi reagent and TeCl4. X-ray crystallographic analyses of 14 revealed distorted pseudo-trigonal-bipyramidal (TBP) structures for Ar4Te and the TBP character was analyzed by the dihedral angle method.

      DOI: 10.1246/bcsj.20180380

      Scopus

      researchmap

    • A stable bis(methylene)-λ<sup>4</sup>-selane with a &gt;cSeC&lt; bond containing Se(IV) 査読有り

      K. Sugamata, Y. Urao, M. Minoura

      Chemical Communications55 ( 57 ) 8254 - 8257   2019年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Bis(methylene)-λ4-selane 1, which represents a new class of heteroallenes, was synthesized and isolated as a stable purple crystalline solid. X-ray crystallographic analysis revealed a bent allene-type structure with pseudo C2v symmetry and a bent CSeC moiety that contains a 3-center-4-electron π-bond. The NMR spectrum of 1 shows compelling evidence for a slow rotation of the SeC moieties at room temperature. The 77Se NMR spectrum of 1 contains one signal in the region characteristic for Se(iv) compounds.

      DOI: 10.1039/c9cc04121d

      Scopus

      PubMed

      researchmap

    • Nature of the E⋯E′ interactions (E, E′ = O, S, Se, and Te) at naphthalene 1,8-positions with fine details of the structures: Experimental and theoretical investigations 査読有り

      Satoko Hayashi, Manabu Uegaito, Taro Nishide, Eiichiro Tanaka, Waro Nakanishi, Takahiro Sasamori, Norihiro Tokitoh, Mao Minoura

      New Journal of Chemistry43 ( 36 ) 14224 - 14237   2019年

      詳細を見る

      掲載種別:研究論文(学術雑誌)   出版者・発行元:Royal Society of Chemistry ({RSC})  

      The intrinsic dynamic and static natures of the E⋯E′ interactions at the 1,8-positions of 1-(MeE)-8-(MeE′)C10H6 [1a-1f (E ≠ E′) and 1g-1j (E = E′)] were elucidated with QTAIM-DFA, after structural determination of 1-(PhE)-8-(PhE′)C10H6 (3a-3f), where (E, E′: x) = (O, S: A), (O, Se: b), (O, Te: c), (S, Se: d), (S, Te: e), (Se, Te: f), (O, O: g), (S, S: h), (Se, Se: i) and (Te, Te: j) (χE ≥ χE′). While the AB structures are confirmed for 3a, 3b and 3d-3f, which consist of the np(E)⋯σ∗(E′-CPh) interactions, the structure was BB for 3c, where the E-CR/E′-CR (R = Ph) bond is perpendicular to the naphthyl plane in A and it is placed on the plane in B. While the AB structures are determined by the p(E)-π(Ph) conjugations, the BB structure is by the crystal packing effect. The BA structure with np(E′)⋯σ∗(E-CPh) was not detected. While the nature of a typical hydrogen bond with covalency was predicted for BB, AA and BA, with the CT-MC (molecular complex formation through charge transfer) nature for AB in 1e and 1f (R = Me for E-CR/E′-CR), the CT-MC nature was predicted for all conformers of 1j, for example. NBO analysis for 1a-1f revealed that the acceptor orbitals contribute much more than the donor orbitals and the order is σ∗(O-CMe: <0.5 kcal mol-1) ≪ σ∗(S-CMe: ≈5 kcal mol-1) ≪ σ∗(Se-CMe: ≈10 kcal mol-1) ≪ σ∗(Te-CMe: ≈16 kcal mol-1) for np(S), np(Se) and np(Te). The E(2) values proportionally correlate to Cii-1 for AB and/or BA of 1a-1j, if analyzed separately for σ∗(S-C), σ∗(Se-C) and σ∗(Te-C).

      DOI: 10.1039/c9nj02198a

      Scopus

      researchmap

    • Double aromaticity arising from σ- and π-rings 査読有り

      Shunsuke Furukawa, Masahiro Fujita, Yoshihiko Kanatomi, Mao Minoura, Miho Hatanaka, Keiji Morokuma, Kazuya Ishimura, Masaichi Saito

      Communications Chemistry1 ( 1 )   2018年12月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Aromaticity has been a central concept in chemistry since the discovery of benzene in the 19th century and has impacted the science of delocalized π-electron systems. The aromaticity of conventional aromatic compounds usually originates from electron delocalization through a single ring that consists of π-symmetric orbitals. Although double aromaticity, i.e. aromaticity composed of two circularly delocalized orbitals, has been theoretically predicted for over 20 years, the double aromaticity of a bench-stable compound is not well explored by experiment. Here we report the synthesis and isolation of the dication of hexakis(phenylselenyl)benzene, as well as its double aromaticity based on structural, energetic, and magnetic criteria. In this dication, cyclic σ-symmetric and π-symmetric delocalized orbitals are formally occupied by ten and six electrons, respectively, and the aromaticity thus follows the 4n + 2 (n = 1, 2,…) electron Hückel rule, regardless of the σ-orbital or π-orbital symmetry.

      DOI: 10.1038/s42004-018-0057-4

      Scopus

      researchmap

    • Hydrolysis of Phosphonothioates with a Binaphthyl Group: P-Stereogenic O-Binaphthyl Phosphonothioic Acids and Their Use as Optically Active Ligands and Chiral Discriminating Agents 査読有り 国際誌

      Kuwabara Kazuma, Maekawa Yuuki, Minoura Mao, Murai Toshiaki

      ORGANIC LETTERS20 ( 5 ) 1375 - 1379   2018年3月2日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      DOI: 10.1021/acs.orglett.8b00147

      Scopus

      PubMed

      researchmap

    • Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers 査読有り

      Satoshi Omomo, Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      Angewandte Chemie130 ( 14 ) 3859   2018年3月

      詳細を見る

      出版者・発行元:Wiley  

      DOI: 10.1002/ange.201800471

      researchmap

    • Synthesis of a peripherally extended triptycyl group as an aliphatic steric protection group and its application to the kinetic stabilization of an aliphatic sulfenic acid<sup>#</sup> 査読有り

      Mariko Yukimoto, Ryohei Nishino, Fumiaki Suzuki, Michihiro Ishihara, Koh Sugamata, Mao Minoura

      Chemistry Letters47 ( 4 ) 425 - 428   2018年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Trp*, a novel triptycene (Trp)-based aliphatic steric protection group was synthesized, and its potential to offer kinetic stabilization by steric protection was evaluated in the context of synthesizing a sulfenic acid (RSOH), i.e., a highly reactive sulfur-containing species. The isolated sulfenic acid Trp*SOH is thermally very stable, which clearly demonstrates the steric protection provided by Trp*.

      DOI: 10.1246/cl.171230

      Scopus

      researchmap

    • The synthesis of a novel bulky primary alkyl group and its application toward the kinetic stabilization of a tetraalkyldisilene 査読有り

      Mariko Yukimoto, Mao Minoura

      Bulletin of the Chemical Society of Japan91 ( 4 ) 585 - 587   2018年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      A novel, peripherally extended sterically demanding primary alkyl group based on the triptycene (Trp) framework, Trp∗CH2, was designed and synthesized via a convenient one-pot reaction using the Friedel-Crafts alkylation of the corresponding TrpCH2 precursor. The introduction of the Trp∗CH2 groups onto a Si=Si double bond allowed isolating the first stable tetraalkyldisilene that contains primary alkyl groups.

      DOI: 10.1246/bcsj.20170422

      Scopus

      researchmap

    • Heterobimetallic triple-decker complexes derived from a dianionic aromatic stannole ligand 査読有り 国際誌

      Masaichi Saito, Naoki Matsunaga, Jumpei Hamada, Shunsuke Furukawa, Mao Minoura, Susann Wegner, Juri Barthel, Christoph Janiak

      Dalton Transactions47 ( 27 ) 8892 - 8896   2018年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A neutral heterobimetallic triple-decker stannole complex was prepared by the reaction of an anionic ruthenocene bearing a stannole dianionic ligand with [Rh(cod)Cl]2 (cod = 1,5-cyclooctadiene), and the resulting Ru-Rh complex exhibits an electronic property different from those of the corresponding Ru-Ru and Rh-Rh complexes. The Ru-Rh complex can be decomposed in ionic liquids to metal nanoparticles.

      DOI: 10.1039/C8DT01455H

      Scopus

      PubMed

      researchmap

    • Group 2 metal bis(arenecarbochalcogenoate)(crown ether) complexes: Isolation and structural analysis 査読有り 国際誌

      Yoshiharu Tatematsu, Shinzi Kato, Norio Nakata, Masahiro Ebihara, Osamu Niyomura, Koh Sugamata, Mariko Yukimoto, Mao Minoura

      Dalton Transactions47 ( 29 ) 9787 - 9794   2018年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A series of Group 2 metal bis(arenecarbochalcogenoato)(crown ether) complexes M(EE′CAr)2(L)(L′)x (M = Mg, Ca, Sr, Ba; Ar = aryl; E = S, Se; E′ = O, S; L = H2O or THF; L′ = 15-crown-5, 18-crown-6) were synthesized and their structures were revealed by X-ray analyses. The two carbothioato ligands in Mg, Ca and Sr 15-crown-5 complexes are located on the same side of the crown ether plane, while those in Mg, Ca, Sr, and Ba 18-crown-6 compounds are on both sides of the 18-crown-6 plane (trans relative to the plane). For the Ca 15-crown-5 complex, both carbothioato ligands are connected to the central Ca ion through an oxygen atom in a monodentate manner, and the two hydrogen atoms of the coordinated water molecule are intramolecularly hydrogen-bonded with thiocarbonyl sulfur atoms. One of the two carbothioate groups in the Ca 18-crown-6 complex is connected in a bidentate manner to the central metal, while the other is connected in a monodentate manner through an oxygen atom. The two thiocarboxylato ligands in the Sr 15-crown-5 congener are connected in a bidentate fashion to the same side of the crown ether plane. The Ca and Sr compounds are the first examples of alkali earth metal carbochalcogenoate complexes in which carbochalcogenolato ligands are connected in a monodentate manner through an oxygen atom. Both chalcogenoato ligands in Ba(SOCC6H4Me-4)2(18-crown-6) and Sr(SeOCC6H4Me-4)2(18-crown-6) are coordinated in a bidentate manner to the central metal ion.

      DOI: 10.1039/c8dt01959b

      Scopus

      PubMed

      researchmap

    • β-Functionalization of 5,15-Diazaporphyrins with Phosphorus, Oxygen, and Sulfur-Containing Substituents 査読有り

      Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      Bulletin of the Chemical Society of Japan91 ( 8 ) 1264 - 1266   2018年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Chemical Society of Japan  

      DOI: 10.1246/bcsj.20180123

      Scopus

      researchmap

    • Regioselective Functionalization at the 7-Position of 1,2,3-Triphenyl[b]benzophosphole Oxide via P=O-Directed Lithiation 査読有り 国際誌

      Ayana Wakatsuki, Mariko Yukimoto, Mao Minoura, Kaori Fujii, Yoshifumi Kimura, Yoshihiro Matano

      Dalton Transactions47 ( 21 ) 7123 - 7127   2018年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Royal Society of Chemistry  

      DOI: 10.1039/c8dt01503a

      Scopus

      PubMed

      researchmap

    • Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers 査読有り 国際誌

      Satoshi Omomo, Takuma Sugai, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      Angewandte Chemie International Edition57 ( 14 ) 3797 - 3800   2018年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      DOI: 10.1002/anie.201800471

      Scopus

      PubMed

      researchmap

    • Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20 pi, 19 pi, and 18 pi 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids 査読有り 国際誌

      Keisuke Sudoh, Takaharu Satoh, Toru Amaya, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      CHEMISTRY-A EUROPEAN JOURNAL23 ( 64 ) 16364 - 16373   2017年11月

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      In spite of significant advances in redox-active porphyrin-based materials and catalysts, little attention has been paid to 20 pi and 19 pi porphyrins because of their instability in air. Here we report the meso-modification of 5,10,15,20-tetraarylporphyrin with two nitrogen atoms, which led to redox-switchable 20 pi, 19 pi, and 18 pi 5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs). Three kinds of metal(II) complexes and free bases of TADAP were prepared by the metal-templated annulation of the corresponding metal-bis(dipyrrin) complexes. The inductive and resonance effects of the meso-nitrogen atoms on the aromatic, optical, electrochemical, and magnetic properties of the entire TADAP pi-systems were assessed by using various spectroscopic measurements and density functional theory calculations. The aromaticity and pi-pi* electronic transition energies of the TADAPs varied considerably, and were shown to be dependent on the oxidation states of the pi-systems. In contrast to the isoelectronic 5,10,15,20-tetraarylporphyrin derivatives, the 20 pi and 19 pi TADAPs were chemically stable under air. In particular, the 19 pi TADAP radical cations were extremely stable towards dioxygen, moisture, and silica gel. This reflected the low-lying singly occupied molecular orbitals of their pi-systems and the efficient delocalization of their unshared electron spin. The capability of MgTADAP to catalyze aerobic biaryl formation from aryl Grignard reagents was demonstrated, which presumably involved a 19 pi/20 pi redox cycle.

      DOI: 10.1002/chem.201703664

      Scopus

      PubMed

      researchmap

    • Anisotropic Crystals Based on a Main-Group Coordination Polymer with Alignment of Rigid π Skeletons 査読有り

      Masaichi Saito, Tomoki Akiba, Shunsuke Furukawa, Mao Minoura, Masahiko Hada, Hiroshi Y. Yoshikawa

      Organometallics36 ( 14 ) 2487 - 2490   2017年7月24日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      We succeeded in the alignment of π skeletons, resulting in the formation of anisotropic crystals. The combination of plumbacyclopentadienylidene, which has a divalent lead atom incorporated into the π skeleton, and 1,4-dioxane afforded a coordination polymer, where the π skeletons are completely aligned in the same direction. The resulting plumbylene chains are also aligned in the same direction in the solid state, and therefore the crystals are noncentrosymmetric, showing second-harmonic generation (SHG) properties. Using pyrazine instead of 1,4-dioxane afforded an adduct composed of three plumbole units and two pyrazine molecules, and the crystals are symmetric and exhibit no SHG properties. The solid-state structures and optical properties are highly dependent on the Lewis base utilized. The present findings spotlight the use of group 14 divalent species incorporated into a π skeleton as a novel, useful method for the creation of a π-aligned coordination polymer with NLO properties.

      DOI: 10.1021/acs.organomet.7b00217

      Scopus

      researchmap

    • Nitrogen-Bridged Metallodiazaporphyrin Dimers: Synergistic Effects of Nitrogen Bridges and meso-Nitrogen Atoms on Structure and Properties 査読有り 国際誌

      Masahiro Kawamata, Takuma Sugai, Mao Minoura, Yasuhisa Maruyama, Ko Furukawa, Cole Holstrom, Victor N. Nemykin, Haruyuki Nakano, Yoshihiro Matano

      CHEMISTRY-AN ASIAN JOURNAL12 ( 7 ) 816 - 821   2017年4月

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      NH-bridged and pyrazine-fused metallodiazaporphyrin dimers have been prepared from nickel(II) and copper(II) complexes of 3-amino-5,15-diazaporphyrin by Pd-catalyzed C-N cross-coupling and oxidative dimerization reactions, respectively. The synergistic effects of the nitrogen bridges and meso-nitrogen atoms play major roles in enhancing the light-harvesting properties and delocalization of an electron spin over the entire pi-skeletons of the metallodiazaporphyrin dimers.

      DOI: 10.1002/asia.201700204

      Scopus

      PubMed

      researchmap

    • Synthesis and reactivity of a ruthenocene-type complex bearing an aromatic π-ligand with the heaviest group 14 element 査読有り 国際誌

      Marisa Nakada, Takuya Kuwabara, Shunsuke Furukawa, Masahiko Hada, Mao Minoura, Masaichi Saito

      Chemical Science8 ( 4 ) 3092 - 3097   2017年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      An anionic ruthenocene derived from a dilithioplumbole complex was prepared. In the complex, the plumbole ligand coordinates a ruthenium atom in an η5-fashion, similar to the cyclopentadienyl ligand in ferrocene. The ruthenocene that has the aromatic π-ligand with the heaviest group 14 element reacted with electrophiles to afford the plumbole complexes wherein the plumbole ligands show deviation from planarity, in contrast to the planar plumbole ring in the anionic ruthenocene. The bent angles of the plumbole ligands are dependent on the substituents on the lead atoms. Cyclic voltammetry measurements revealed that the plumbole complexes are oxidized more easily than the corresponding stannole complexes.

      DOI: 10.1039/c6sc04843a

      Scopus

      PubMed

      researchmap

    • Nitrogen-Bridged Metallodiazaporphyrin Dimers: Synergistic Effects of Nitrogen Bridges and meso-Nitrogen Atoms on Structure and Properties 査読有り 国際誌

      Masahiro Kawamata, Takuma Sugai, Mao Minoura, Yasuhisa Maruyama, Ko Furukawa, Cole Holstrom, Victor N. Nemykin, Haruyuki Nakano, Yoshihiro Matano

      Chemistry-An Asian Journal12 ( 7 ) 816 - 821   2017年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      DOI: 10.1002/asia.201700204

      PubMed

      researchmap

    • Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20π, 19π, and 18π 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids 査読有り 国際誌

      Keisuke Sudoh, Takaharu Satoh, Toru Amaya, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano

      Chemistry-A European Journal23 ( 64 ) 16364 - 16373   2017年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      DOI: 10.1002/chem.201703664

      PubMed

      researchmap

    • A Self-Assembled Rectangular Host with Terpyridine-Platinum(II) Moieties That Binds Unsubstituted Pentacene in Solution 査読有り

      Yusuke Yamaki, Takashi Nakamura, Sayuri Suzuki, Masaki Yamamura, Mao Minoura, Tatsuya Nabeshima

      European Journal of Organic Chemistry2016 ( 9 ) 1678 - 1683   2016年3月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Pentacene has attracted much attention as an organic electric material, but it often suffers from its very low solubility. We now report self-assembled rectangular host 18+ that has two pairs of terpyridine-PtII moieties aligned parallel to each other and connected by diyne linkers. The host encapsulated unsubstituted pentacene (2) with a remarkably strong binding constant of Ka ≈ 107 M-1 and solubilized it in acetonitrile up to the millimolar level. For smaller acenes (i.e., naphthalene to tetracene), a planar arrangement of two molecules inside the cavity was achieved. These results made it possible to analyze the acenes in the solution phase and provided a way to align the guests by a solution-processing method as a possible application, and thus, they contribute to fundamental physical organic chemistry as well as organic electronics.

      DOI: 10.1002/ejoc.201600058

      Scopus

      researchmap

    • Redox-Switchable 20π-, 19π-, and 18π-Electron 5,10,15,20-Tetraaryl-5,15-diazaporphyrin -oid Nickel(II) Complexe 査読有り 国際誌

      Satoh T, Minoura M, Nakano H, Furukawa K, Matano Y

      Angewandte Chemie International Edition55 ( 6 ) 2235 - 2238   2016年2月5日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Wiley  

      DOI: 10.1002/anie.201510734

      PubMed

      researchmap

    • Redox-Switchable 20-, 19-, and 18-Electron 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoid Nickel(II) Complexes 査読有り

      Takaharu Satoh, Mao Minoura, Haruyuki Nakano, Ko Furukawa, Yoshihiro Matano

      ANGEWANDTE CHEMIE-INTERNATIONAL EDITION55 ( 6 ) 2235 - 2238   2016年2月

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      The first examples of air-stable 20-electron 5,10,15,20-tetraaryl-5,15-diaza-5,15-dihydroporphyrins, their 18-electron dications, and the 19-electron radical cation were prepared through metal-templated annulation of nickel(II) bis(5-arylamino-3-chloro-8-mesityldipyrrin) complexes followed by oxidation. The neutral 20-electron derivatives are antiaromatic and the cationic 18-electron derivatives are aromatic in terms of the magnetic criterion of aromaticity. The meso Natoms in these diazaporphyrinoids give rise to characteristic redox and optical properties for the compounds that are not typical of isoelectronic 5,10,15,20-tetraarylporphyrins.

      DOI: 10.1002/anie.201510734

      Scopus

      researchmap

    • Phosphonoselenoic acid esters from the reaction between phosphoroselenoyl chlorides and Grignard reagents: synthetic and stereochemical aspects 査読有り

      Toshiaki Murai, Yuuki Maekawa, Yuuki Hirai, Kazuma Kuwabara, Mao Minoura

      RSC ADVANCES6 ( 18 ) 15180 - 15183   2016年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

      Substitution reactions between a phosphoroselenoyl chloride and Grignard reagents proceeded smoothly at the phosphorus atom to furnish phosphonoselenoic acid esters. The resulting mixture of diastereoisomers could be readily distinguished on the basis of P-31 NMR, and separated by recrystallization or column chromatography to afford diastereoisomerically enriched products. For one of these diastereoisomers, the absolute configuration was determined by carrying out a single-crystal X-ray diffraction analysis.

      DOI: 10.1039/c6ra00318d

      Scopus

      researchmap

    • A reversible two-electron redox system involving a divalent lead species 国際誌

      Masaichi Saito, Marisa Nakada, Takuya Kuwabara, Mao Minoura

      Chemical Communications51 ( 22 ) 4674 - 4676   2015年3月18日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Reduction of THF-stabilized plumbacyclopentadienylidene with lithium afforded dilithioplumbole. On the other hand, oxidation of the dilithioplumbole provided the starting plumbacyclopentadienylidene. This is the unprecedented example of a reversible interconversion between group 14 M(ii) and its dianionic species bearing organic substituents. This journal is

      DOI: 10.1039/c4cc09856k

      Scopus

      PubMed

      researchmap

    • Unexpected dehalogenation reactions of dichloroborane bearing a NCN-pincer ligand: Formation of a borenium salt

      Masaichi Saito, Kaori Matsumoto, Masahiro Fujita, Mao Minoura

      Heteroatom Chemistry25 ( 5 ) 354 - 360   2014年11月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      2,6-Bis[(diisopropylamino)methyl]phenyllithium 1 reacted with trichloroborane etherate to afford dichloroarylborane 4. The treatment of 4 with Ag triflate provided bistriflate 5. The reaction of 4 with AgBF<inf>4</inf>, however, afforded an unexpected product, borenium salt 6.

      DOI: 10.1002/hc.21211

      Scopus

      researchmap

    • Synthesis, structure, and thermolysis of tetracoordinated 1λ<sup>4</sup>,2-selenazetidines bearing two chiral centers at the 3-and 4-positions

      Yuya Daicho, Naokazu Kano, Mariko Yukimoto, Mao Minoura, Takayuki Kawashima

      Heteroatom Chemistry25 ( 5 ) 492 - 499   2014年11月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The title trans and cis isomers (trans-3 and cis-3) were successfully synthesized as stable compounds by taking advantage of the Martin ligand. The X-ray crystallographic analysis of trans-3 showed that it has a distorted pseudotrigonal bipyramidal structure, and that the two phenyl groups at the 3-and 4-positions are cis to each other. The thermolysis of trans-3 in the presence of excess dimethyl acetylenedicarboxylate (DMAD) gave a mixture of the corresponding aziridines (trans-7 and cis-7) and cycloadducts (11a and 11b) of the azomethine ylides formed by ring opening of the aziridines with DMAD. Heating of cis-7 and excess DMAD under the same conditions gave diastereomeric mixtures of both the aziridines and the cycloadducts, which means that the stereochemistry of the aziridine formation from the 1,2-selenazetidine cannot be determined in this system.

      DOI: 10.1002/hc.21177

      Scopus

      researchmap

    • Enhancement of stannylene character in stannole dianion equivalents evidenced by NMR and Mössbauer spectroscopy and theoretical studies of newly synthesized silyl-substituted dilithiostannoles

      Takuya Kuwabara, Jing Dong Guo, Shigeru Nagase, Mao Minoura, Rolfe H. Herber, Masaichi Saito

      Organometallics33 ( 11 ) 2910 - 2913   2014年6月9日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Dilithiostannoles, which are aromatic tin-containing ring compounds, were proposed to have stannylene character, as judged from their NMR analysis. We herein report on the synthesis of silyl-substituted dilithiostannoles, which were characterized by NMR spectroscopy and X-ray diffraction analysis. The silyl-substituted derivatives also exhibit features characteristic of aromatic dilithiostannoles such as 7Li NMR signals at high-field area and no C-C bond alternation in the stannole rings. Theoretical calculations and the 119Sn NMR chemical shifts revealed that the stannylene character in the silyl-substituted dilithiostannoles is enhanced due to greater interaction between 5p (Sn) and LUMO (butadiene) in comparison to those in alkyl and aryl derivatives. The 119Sn Mössbauer spectra of dilithiostannoles were measured for the first time, indicating that each of the tin atoms in dilithiostannoles can be characterized as having Sn(II) character. © 2014 American Chemical Society.

      DOI: 10.1021/om5003717

      Scopus

      researchmap

    • Synthesis and structures of monomeric group 14 triols and their reactivity

      Lucian Cristian Pop, Nobuaki Kurokawa, Hiroaki Ebata, Katsuya Tomizawa, Tomoyuki Tajima, Masatoshi Ikeda, Michikazu Yoshioka, Monique Biesemans, Rudolph Willem, Mao Minoura, Masaichi Saito

      Canadian Journal of Chemistry92 ( 6 ) 542 - 548   2014年6月

      詳細を見る

      掲載種別:研究論文(国際会議プロシーディングス)  

      The first stable stannanetriol and germanetriol bearing sterically congested aryl groups were synthesized by hydrolysis of the corresponding trichloro-stannane and-germane.The stannanetriol is monomeric in solution as well as in the crystalline state, as evidenced by X-ray diffraction analysis and CP-MAS NMR spectroscopy.The stannanetriol reacted with silicone grease to afford a cagelike compound having three Sn-O-Si-O-Sn linkages in the molecule.All the group 14 triols can be converted to the corresponding trihalo compounds in good yields.© 2014 Published by NRC Research Press.

      DOI: 10.1139/cjc-2013-0496

      Scopus

      researchmap

    • Aziridine formation with retention of configuration from a pentacoord inated 1, 2-thiazetidine bearing two chiral centers at the 3- And 4-positions

      Yuya Daicho, Yuki Watanabe, Naokazu Kano, Mariko Yukimoto, Mao Minoura, Takayuki Kawashima

      Bulletin of the Chemical Society of Japan87 ( 9 ) 1005 - 1012   2014年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Tetracoordinated and pentacoordinated 1,2-thiazetidines bearing the Martin ligand, trans-5 and trans-6, were synthesized as stable compounds. The X-ray crystallographic analyses showed that trans-5 and trans-6 have distorted pseudotrigonal bipyramidal (pseudo-TBP) and TBP structures, respectively, and that the two phenyl groups at the 3- and 4-positions of both compounds are cis to each other. Thermal isomerization of the aziridine cis-11, which is considered a thermolysis product of trans-6, occurred even at relatively low temperature (100°C) in solution and made it difficult to determine the stereochemistry of the aziridine formation from trans-6 in solution. Flash vacuum pyrolysis, which potentially prevents the isomerization of the product, was applied to trans-6 to give eventually the stereochemistry-retained aziridine cis-11. This result indicates a ligand coupling pathway in the aziridine formation process from trans-6.

      DOI: 10.1246/bcsj.20140132

      Scopus

      researchmap

    • Fluorinative hydrolysis of phosphorothioic acid esters with a binaphthyl group through axis-to-center chirality transfer leading to the formation of P-chiral phosphorothioic monofluoridic acid salts 査読有り 国際誌

      Murai Toshiaki, Hayashi Takae, Yamada Kyohei, Maekawa Yuuki, Minoura Mao

      CHEMICAL COMMUNICATIONS50 ( 83 ) 12473 - 12475   2014年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      DOI: 10.1039/c4cc05198j

      Scopus

      PubMed

      researchmap

    • Synthesis, structure, and reactivity of lewis base stabilized plumbacyclopentadienylidenes 国際誌

      Masaichi Saito, Tomoki Akiba, Misumi Kaneko, Toshiaki Kawamura, Minori Abe, Masahiko Hada, Mao Minoura

      Chemistry - A European Journal19 ( 50 ) 16946 - 16953   2013年12月9日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Plumbacyclopentadienylidenes, in which the lead atoms have divalent states and are coordinated by THF, pyridine and N-heterocyclic carbene, were synthesized and characterized. The THF-and pyridine-stabilized compounds can be regarded as rare examples of hypervalent 10-X-4 species. The equilibrium between the THF adduct and the free plumbacyclopentadienylidene was evidenced by spectroscopic analysis and theoretical calculations. The THF adduct in benzene converted into a plumbylene dimer, where one of the lead centers is coordinated by THF and the other lead atom is coordinated by a divalent lead atom, the dimer gradually decomposing into spiroplumbole. The THF adduct unexpectedly reacted with trifluoroborane and trichlorogallane to afford fluoroborole and chlorogallole, which are the first examples of non-annulated fluoroborole and gallole, respectively. Plumbacyclopentadienylidenes, in which the lead atoms have divalent states and are coordinated by THF, pyridine, and an N-heterocyclic carbene, were synthesized and characterized. The THF-stabilized compound can be regarded as a rare example of hypervalent 10-X-4 species, which converts into a plumbylene dimer and reacts with trifluoroborane and trichlorogallane to afford the corresponding fluoroborole and chlorogallole, respectively (see scheme; R=Me2tBuSi). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

      DOI: 10.1002/chem.201303672

      Scopus

      PubMed

      researchmap

    • Synthesis of new dipyrido-annulated N-heterocyclic carbenes with ortho substituents 国際誌

      Shin Ichi Fuku-En, Junki Yamamoto, Mao Minoura, Satoshi Kojima, Yohsuke Yamamoto

      Inorganic Chemistry52 ( 20 ) 11700 - 11702   2013年10月21日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A method for the introduction of various substituents at the 4 and 8 positions of 2,10-di-tert-butyldipyrido[1,2-c;2′,1′-e]imidazolium salts, is described. The new imidazolium salts bearing substituents (R′ = Cl, SPh) at the 4 and 8 positions are synthesized in three-step procedures, and carbenes generated from the imidazolium salts can be used to give the corresponding rhodium complexes. The role of the 4,8-substituents can be either bystanders or coordinating ligands according to the nature of the metal moiety. © 2013 American Chemical Society.

      DOI: 10.1021/ic402301u

      Scopus

      PubMed

      researchmap

    • Studies on chalcogen-containing heterocycles. Part 38: Regio- and stereoselective tandem addition-iodocyclization of 2-ethynylphenyl isothiocyanates with N- and O-nucleophiles affording 4-(iodoalkylidene)benzo[d] [1,3]thiazines

      Haruki Sashida, Mamoru Kaname, Mao Minoura

      Tetrahedron69 ( 31 ) 6478 - 6487   2013年8月5日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The treatment of the o-ethynylphenyl isothiocyanates with primary and secondary amines in 1,2-DCE, followed by the addition of I2 and then heating resulted in the regio- and stereoselective tandem addition- iodocyclization to give the (4E)-2-amino-4-(1-iodomethylidene)benzo[d][1,3] thiazine derivatives as the sole product in high yields via the 6-exo-dig mode cyclization. The 2-alkoxy-1,3-benzothiazines were similarly produced from the o-ethynylphenyl isothiocyanates and the corresponding sodium alkoxides. © 2013 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.tet.2013.05.069

      Scopus

      researchmap

    • Studies on chalcogen-containing heterocycles. Part 37: M-CPBA oxidation of isotellurochromenes and isoselenochromenes

      Haruki Sashida, Mamoru Kaname, Kazuo Ohyanagi, Mao Minoura

      Tetrahedron68 ( 51 ) 10502 - 10509   2012年12月23日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The oxidation of the 1-unsubstituted isotellurochromenes and isoselenochromenes with m-CPBA resulted in a novel ring-opening reaction to give the o-formyl distyryl ditellurides and diselenides as the sole products in good yields, respectively. The o-benzoyl distyryl ditelluride and diselenide were also produced from the corresponding 1-phenylisochromenes. In contrast, the 1-benzyl and 1-n-butylisochromenes were oxidized to afford the (Z)-1-benzylideneisochromenes and (Z)-1-butylideneisochromenes under similar conditions; no distyryl compounds were obtained. The distyryl compounds were also obtained by the hydrolysis of the corresponding 2-benzochalcogenopyrylium salts, which were easily converted from the 2-benzoisochromenes by treatment with triphenylcarbenium tetrafluoroborate (Ph 3C+BF 4-). © 2012 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.tet.2012.07.023

      Scopus

      researchmap

    • Synthesis, structures, and optical properties of heterasumanenes containing group 14 elements and their related compounds

      Tomoharu Tanikawa, Masaichi Saito, Jing Dong Guo, Shigeru Nagase, Mao Minoura

      European Journal of Organic Chemistry ( 36 ) 7135 - 7142   2012年12月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Triphenylenogermole, triphenylenodigermole, and trigermasumanene were prepared by repetitive lithiation of triphenylene followed by introduction of germanium functionalities. This is the first example of a trigermasumanene. Tin congeners were also synthesized and investigated. X-ray diffraction analysis of trisilasumanene 6, which does not have any substituents on the carbon atoms of the benzene rings, is also demonstrated. The optical properties of trigermasumanene and its derivatives were investigated by UV/Vis and fluorescence spectroscopy. Theoretical calculations were carried out to understand the properties of the thus-obtained triphenylenometallole derivatives. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

      DOI: 10.1002/ejoc.201201223

      Scopus

      researchmap

    • Molecular structure and electronic state of the dibenzo[a,e]pentalene anion radical 国際誌

      Masaichi Saito, Yoko Hashimoto, Tomoyuki Tajima, Kazuya Ishimura, Shigeru Nagase, Mao Minoura

      Chemistry - An Asian Journal7 ( 3 ) 480 - 483   2012年3月5日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Undergoing a radical change! The reduction of dibenzo[a,e]pentalene by KC 8 afforded the corresponding anion radical, the structure of which was characterized for the first time by X-ray diffraction analysis. The electronic state of the anion radical is discussed with the aid of theoretical calculations. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

      DOI: 10.1002/asia.201100711

      Scopus

      PubMed

      researchmap

    • 2D s-d mixed-metal coordination polymer containing potassium, chromium(III) and dipicolinate ions: Preparation and crystal structure

      Mohammad Hakimi, Boris Marko Kukovec, Mao Minoura

      Journal of Chemical Crystallography42 ( 3 ) 290 - 294   2012年3月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The reaction of pyridine-2,6-dicarboxylic acid (dipicolinic acid, dipicH2) with potassium tetraperoxochromate( V) in the mixture of water and ethanol led to the formation of a 2D s-d mixed-metal coordination polymer of {K[Cr(dipic)2]}n (1). The compound was characterized by spectroscopic methods (IR, Raman, UV/Vis). Single crystal X-ray diffraction analysis revealed that dipicolinate ligand is coordinated to the chromium(III) ion in an O,N,O0-tridentate fashion, while its uncoordinated and coordinated carboxylate O atoms (with respect to Cr(III) ion) are in turn bound to potassium ions. Therefore, each dipicolinate ligand bridges two potassium ions and a chromium(III) ion between them, giving rise to a 2D coordination network. The coordination of chromium(III) ions is octahedral, while the coordination number of potassium ions is 8. The coordination networks are in turn assembled only by π-π stacking interactions into a 3D structure. © The Author(s) 2011.

      DOI: 10.1007/s10870-011-0242-0

      Scopus

      researchmap

    • Synthesis, characterization and crystal structure of a binuclear cadmium iodide complex with a multi-N-donor oxazolidine ligand

      Mohammad Hakimi, Zahra Mardani, Keyvan Moeini, Mao Minoura, Heidar Raissi

      Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences66 ( 11 ) 1122 - 1126   2011年11月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The ligand, 2-(2-(pyridin-2-yl)oxazolidin-3-yl)-N-(pyridin-2-ylmethylene) ethanamine, POPME, was prepared via microwave-supported Schiff base and oxazolidination reactions. The cadmium iodide complex [Cd2(POPME) (μ-I)2I2] was prepared and identified by elemental analysis, IR, Raman and 1H and 13C NMR spectroscopy and single-crystal X-ray diffraction. In the crystal structure two Cd(II) ions with coordination numbers four and six are bridged by two iodide anions. Cd 1 and Cd2 have distorted octahedral CdI2N 4 and tetrahedral CdI4 geometries, respectively.Weak intermolecular hydrogen bonds H⋯I and H⋯O stabilize the supramolecular network. © 2011 Verlag der Zeitschrift für Naturforschung, Tübingen.

      DOI: 10.1515/znb-2011-1106

      Scopus

      researchmap

    • One-pot copper-catalyzed tandem addition-cyclization of 2-iodoanilines with isoselenocyanates for the practical preparation of 2-aminobenzoselenazoles

      Mamoru Kaname, Mao Minoura, Haruki Sashida

      Tetrahedron Letters52 ( 4 ) 505 - 508   2011年1月26日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      A convenient and successful one-pot preparation of the 2- aminobenzoselenazoles via the phenylselenoureas has been accomplished by the copper-catalyzed ligand-free reaction of the 2-iodoanilines and isoselenocyanates; the intermediate, selenoureas, were isolated, and quantitatively transformed into the selenazaoles. © 2010 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.tetlet.2010.11.092

      Scopus

      researchmap

    • Reaction of 2-(aminomethyl)pyridine with selenium dioxide: Synthesis and structure of selenium-bridged imidazo[1,5-a]pyridine derivatives

      Osamu Niyomura, Yoshimi Yamaguchi, Souhei Tamura, Mao Minoura, Yoshihisa Okamoto

      Chemistry Letters40 ( 5 ) 449 - 451   2011年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Reaction of 2-(aminomethyl)pyridine with selenium dioxide leads to the formation of imidazo[1,5-a]pyridine (2-azaindolizin6) skeleton in a single step. The major products of the reactions are 3-(2-pyridyl)imidazo[1,5-a]pyridine, bis[3-(2-pyridyl) imidazo[1,5-a]pyridin-1-yl] selenide, or the corresponding diselenide depending upon the reaction conditions. The structures of these selenium-bridged imidazo[1,5-a]pyridine derivatives are disclosed by X-ray crystal structural analyses. For the diselenide, the unusual dihedral angle CSeSeC of 56.0° was observed indicating π-π intramolecular interaction between the fused six-membered rings. © 2011 The Chemical Society of Japan.

      DOI: 10.1246/cl.2011.449

      Scopus

      researchmap

    • Regioselective electrophilic cyclization of o-ethynylbenzyl phenyl selenides to (Z)-1-methylidene-2-phenyl-1,3-dihydro-1H-benzo[c]selenophenium salts

      Haruki Sashida, Shoko Nakabayashi, Hirokazu Suzuki, Mamoru Kaname, Mao Minoura

      Tetrahedron Letters51 ( 41 ) 5395 - 5398   2010年10月13日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      o-Ethynylbenzyl phenyl selenides regioselectively reacted with trifluoromethanesulfonic acid to afford the (Z)-1-methylidene-2-phenyl-1,3- dihydro-1H-benzo[c]selenophenium salts as the major products during the 5-exo-dig mode cyclization in good yields together with minor E isomers. The structure of the major (Z)-selenophenium salt was established by the single crystal X-ray crystallographic analysis using a tert-butyl derivative. © 2010 Elsevier Ltd. All rights reserved.

      DOI: 10.1016/j.tetlet.2010.07.160

      Scopus

      researchmap

    • A straightforward double intramolecular cyclization of dibenzyl dichalcogenols into a triple bond

      Haruki Sashida, Mamoru Kaname, Akemi Nakayama, Hirokazu Suzuki, Mao Minoura

      Tetrahedron66 ( 27-28 ) 5149 - 5157   2010年7月3日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The intramolecular cyclizations of four types of dibenzyl chalcogenols, which contained one or two ethynyl groups, were carried out. Either the double 5-exo or 6-endo-dig mode ring closure reaction regio- and stereoselectively proceeded to give the corresponding symmetrical bis(benzoc1chalcogeno- phene) or bis(isochromene) derivatives from the dibenzyl chalcogenols having a diyne moiety. In contrast, the regioselective tandem 5-exo-dig mode intramolecular ring closure reactions of dibenzyl thiol and selenol having a mono-yne into a triple bond gave the trans-biisobenzothiophene and selenophene as the sole product. However, the similar cyclization of dibenzyl tellurol proceeded in both tandem 5-exo and 6 endo dig modes to afford the trans biisobenzotellurophene and ditellurachrysene in good yields with the ratio of 1:1. The X-ray structural analysis of these novel compounds is also presented. © 2010 Elsevier Ltd.

      DOI: 10.1016/j.tet.2010.04.101

      Scopus

      researchmap

    • Synthesis, structure, spirocyclization mechanism, and glutathione peroxidase-like antioxidant activity of stable spirodiazaselenurane and spirodiazatellurane 国際誌

      Bani Kanta Sarma, Debasish Manna, Mao Minoura, Govindasamy Mugesh

      Journal of the American Chemical Society132 ( 15 ) 5364 - 5374   2010年4月

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      The first examples of stable spirodiazaselenurane and spirodiazatellurane were synthesized by oxidative spirocyclization of the corresponding diaryl selenide and telluride and were structurally characterized. X-ray crystal structures of the spirodiazaselenurane and spirodiazatellurane suggest that the structures are distorted trigonal bipyramidal (TBP) with the electronegative nitrogen atoms occupying the apical positions and two carbon atoms and the lone pair of Se/Te occupying the equatorial positions. Interestingly, the spirodiazatellurane underwent spontaneous chiral resolution during crystallization, and the absolute configurations of its enantiomers were confirmed by single-crystal X-ray analyses. A detailed mechanistic study indicates that the cyclization to spirodiazaselenurane and spirodiazatellurane occurs via selenoxide and telluroxide intermediates. The chalcogenoxides cyclize to the corresponding spiro compounds in a stepwise manner via the involvement of hydroxyl chalcogenurane intermediates, and the activation energy for the spirocyclization reaction decreases in the order S > Se > Te. In addition to the synthesis, characterization, and mechanism of cyclization, the glutathione peroxidase (GPx) mimetic activity of the newly synthesized compounds was evaluated. These studies suggest that the tellurium compounds are more effective as GPx mimics than their selenium counterparts due to the fast oxidation of the tellurium center in the presence of peroxide and the involvement of an efficient redox cycle between the telluride and telluroxide intermediate. © 2010 American Chemical Society.

      DOI: 10.1021/ja908080u

      Scopus

      PubMed

      researchmap

    • 2-Substituted isotellurochromenium salt derivatives: Preparations, structures, spectroscopic properties

      Haruki Sashida, Shoko Nakabayashi, Mamoru Kaname, Mao Minoura

      Heterocycles80 ( 2 ) 1339 - 1352   2010年3月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Several types of novel isotellurochromenium salt derivatives (210) were prepared from the isotellurochromenes (1). The isotellurochromenium tetrafluoroborates (2), triflates (35), tosylates (6) and mesylates (7) are telluronium salts, and the dihalogenoisotellurochromenes (810) are telluranes. The molecular structures of the isotellurochromenium tosylate (6a) and the dichloroisotellurochromene (8a) were characterized by an X-ray crystallographic analysis using the 3-tert-butyl derivatives. © 2010 The Japan Institute of Heterocyclic Chemistry Received.

      DOI: 10.3987/COM-09-S(S)124

      Scopus

      researchmap

    • A facile and practical solvent-free one-pot synthesis of (Z)-4-methylene-3-selenaquinoline derivatives from o-ethynylanilines and isoselenocyanates

      Haruki Sashida, Chao Pan, Mamoru Kaname, Mao Minoura

      Synthesis ( 18 ) 3091 - 3096   2010年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Heating of o-ethynylanilines with isoselenocyanates directly resulted in the 6-exo-dig mode ring-closure reaction of the adducts to give the (Z)-2-imino-4-methylene-3-selenaquinolines in moderate to good yields. Based on this convenient, solvent-free, catalyst-free method, several 3-selenaquinoline derivatives (3,1-benzoselenazines) were easily obtained in one pot. Successful application of the microwave-assisted synthesis of these compounds was also investigated. © Georg Thieme Verlag Stuttgart - New York.

      DOI: 10.1055/s-0030-1258171

      Scopus

      researchmap

    • Evidence for effective p(Z)-π(Ar) conjugations (Z = S, Se, and Te, as well as Z = O) in 9-(Arylchalcogenyl)triptycenes: Experimental and theoretical investigations 国際誌

      Satoko Hayashi, Takashi Nakamoto, Mao Minoura, Waro Nakanishi

      Journal of Organic Chemistry74 ( 13 ) 4763 - 4771   2009年7月3日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      (Chemical Equation Presented) The p(Z)-π(Ar) conjugations must operate fully in the ground states of 9-(arylchalcogenyl)triptycenes (p-YC 6H4ZTpc:1 (Z = O), 2 (Z = S), 3 (Z = Se), and 4 (Z = Te)), where the p-YC6H4 group is placed in the bisected area between two phenyl planes of the triptycyl group with the parallel orientation. The ground-state geometries, which we call (A: pl), are confirmed by X-ray analysis. However, the conjugations never operate in the transition states between (A: pl) and/or the topomeric structures (A′: pl′), where the Z-CTpc bond is perpendicular to the plane. The site-exchange processes correlate to the conjugations. Temperature-dependent 1H NMR spectra are analyzed for 2 and 3 to demonstrate the effective p(Z)-π(Ar) conjugations. The activation energies for the interconversion between (A: pl) and (A′: pl′) (GR: gear process) were obtained for 2 (ΔG ‡GR(2)) and 3 (ΔG‡GR(3)). ΔG‡GR(3) correlate well with ΔG‡GR(2), and ΔG ‡GR(2) are well analyzed by the Hammett-type dual parameters. ΔG‡GR(2) and ΔG ‡GR(3) are demonstrated to be controlled by the resonance interaction of the p(Z)-π(C6H4)-p(Y) conjugations. QC calculations are performed on the ground and exited states of 1-4, which clarify the effective p(Z)-π(C6H4)-p(Y) conjugations for Z of heavier atoms. © 2009 American Chemical Society.

      DOI: 10.1021/jo900488r

      Scopus

      PubMed

      researchmap

    • Chemistry of 1-Benzotelluropyrylium salts: Synthesis, structure and reactions

      Haruki Sashida, Mao Minoura

      Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry67 ( 7 ) 714 - 723   2009年7月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The three main parts; i.e., the preparations, structures and reactions of the 1-benzotelluropyryli- um salts are described. The synthetic workup has been achieved by transformation from the tel-lurochromones, which were simply prepared by the reaction of the o-bromophenyl ethynyl ketones with sodium hydrogen telluride (NaHTe). The synthetic method for the preparation of the tellurochromones is based on the intramolecular ring closure of a tellurol moiety into a triple bond. The study shows that these salts, although being stable compounds, are highly reactive with various nucleophiles including OMē, diethylamine, CN̄, an active methylene compound and Grignard reagents, and also hydrogenation and hydrolysis to afford the successful corresponding 2- or 4-substituted tellurochromene derivatives. The chemistry of the 1-benzoselenopyrylium salts is also described. The thermolysis of the 2-azidoselenochromenes, which were easily obtained by the reaction of the selenopyrylium salts with sodium azide, resulted in a ring expansion to produce the novel stable 1,3-benzoselenazepines. X-ray structural analyses of the terf-butyltelluro- and selenopyrylium salts are also reported.

      DOI: 10.5059/yukigoseikyokaishi.67.714

      Scopus

      researchmap

    • Structures and dynamic stereochemistry of 9-arylselanyltriptycenes: X-ray crystallographic, spectroscopic and theoretical investigations

      Takashi Nakamoto, Satoko Hayashi, Waro Nakanishi, Mao Minoura, Gaku Yamamoto

      New Journal of Chemistry33 ( 7 ) 1588 - 1595   2009年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      9-(Arylselanyl)triptycenes (1: p-YC6H4SeTpc) should supply the planar structure (pl) around the p-YC6H4Se (ArSe) group in the ground state, irrespective of the p-Y substituents. 1 with Y = H (a), NMe2 (b), OMe (c), Cl (d), CN (e) and NO2 (f) are prepared. Structures of 1a-d and 1f are determined by X-ray analysis and dynamic 1H NMR spectroscopy is applied to 1a, 1c, 1e and 1f. For convenience of discussion, the structure of 1 is defined as follows: a conformer around the triptycyl group in 1 is called A where the Se-CAr bond is placed in the bisected area between two phenyl planes of the triptycyl group and it is B where the bond is on a phenyl plane of the triptycyl group. A conformer for the Ar group is named pl where the Se-CTpc bond is on the Ar plane, while it is pd if the bond is perpendicular to the plane. The structure of 1 is confirmed to be (A: pl) in the ground state by X-ray analysis. 1 (A: pl) changes to the equivalent one via a transition state of 1 (B: pd) (the gear process). The activation energies are determined by dynamic 1H NMR spectroscopy: the values are 36.4, 41.6, 42.3 and <34 kJ mol-1 for 1a, 1e, 1f and 1c, respectively. The MP2 level of calculations reproduced the observed values: they are evaluated to be 34, 39, 40 and 29 kJ mol-1 for 1a, 1e, 1f and 1b′ (Y = NH2), respectively, where 1b′ is employed in place of 1c. Another process (the isolated rotation process) is also operating for the interconversion of 1 (A: pl), which proceeds via1 (A: pd). The activation energies for the process are predicted to be 25, 30, 30 and 20 kJ mol-1 for 1a, 1e, 1f and 1b′, respectively, at the MP2 level. The results demonstrate that (A: pl) is the global minimum in 1: the 1 (A: pl) structure is well established for all Y examined in the ground state. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2009.

      DOI: 10.1039/b817949b

      Scopus

      researchmap

    • One-pot synthesis of indolizine derivative and its application as multi-dentate ligand

      Osamu Niyomura, Yoshimi Yamaguchi, Ryo Sakao, Mao Minoura, Yoshihisa Okamoto

      Heterocycles75 ( 2 ) 297 - 304   2008年2月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      1-Cyano-3-(2-pyridinecarboxamido)-2-(2-pyridiyl)indolizine (2) was readily synthesized by the one-pot reaction of 2-(cyanomethyl)pyridine (1a) with selenium dioxide. The reaction of 3- or 4-(cyanomethyl)pyridines (1b,c) under the same reaction conditions gave 2,3-bi(3-pyridyl)-2-butenedinitrile (3b) and 2,3-bi(4-pyridyl)-2-butenedinitrile (3c), respectively. The indolizine 2 (L-H) reacted with Ni(NO3)2·6H2O in ethanol to produce the NiL2 complex (4). The structure was determined by X-ray crystallography. © 2008 The Japan Institute of Heterocyclic Chemistry.

      DOI: 10.3987/COM-07-11197

      Scopus

      researchmap

    • Synthesis and structural characterization of 1-mesityl-1,3-dihydro- imidazole-2-selone and bis(1-mesitylimidazol-2-yl)diselenide: Experimental evidence that the selone is more stable than the selenol tautomer 国際誌

      Victoria K. Landry, Mao Minoura, Keliang Pang, Daniela Buccella, Bryte V. Kelly, Gerard Parkin

      Journal of the American Chemical Society128 ( 38 ) 12490 - 12497   2006年9月27日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      1-Mesityl-1,3-dihydro-imidazole-2-selone, (seimMes)H, may be obtained from 1-mesitylimidazole via (i) deprotonation with BunLi, (ii) treatment with elemental selenium, and (iii) addition of HCl(aq). Structural characterization of (seimMes)H by X-ray diffraction demonstrates that the compound exists as the selone rather than selenol tautomer, a result that is in accord with DFT calculations. Solutions of (seimMes)H are oxidized by air to give bis(1-mesitylimidazol-2-yl) diselenide, (seimMes)2. A corresponding investigation of (seimMe)H demonstrates that, in contrast to a previous report, the selenium analogue of methimazole exists in the selone form with a structure analogous to that of methimazole. 1H and 77Se NMR studies demonstrate that the (seimR) groups of the selone (seimR)H and diselenide (seimR)2 undergo facile exchange on the NMR time scale. © 2006 American Chemical Society.

      DOI: 10.1021/ja063168e

      Scopus

      PubMed

      researchmap

    • Synthesis and structural characterization of tris(2-seleno-1- mesitylimidazolyl) hydroborato complexes: A new type of strongly electron donating tripodal selenium ligand 国際誌

      Mao Minoura, Victoria K. Landry, Jonathan G. Melnick, Keliang Pang, Luciano Marchiò, Gerard Parkin

      Chemical Communications ( 38 ) 3990 - 3992   2006年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A new tripodal ligand that features three selenium donors, namely the tris(2-seleno-1-mesitylimidazolyl)hydroborato ligand, [TseMes], has been constructed via the reaction of KBH4 with 1-mesitylimidazole-2- selone; comparison of the IR spectroscopic data of [TseMes]Re(CO) 3 with those of a variety of related LRe(CO)3 complexes demonstrates that the [TseMes] ligand is more strongly electron donating than Cp, Cp*, [Tp], [TpMe2] and [Tm Mes] ligands. © The Royal Society of Chemistry 2006.

      DOI: 10.1039/b608078b

      Scopus

      PubMed

      researchmap

    • Deamination of 1-alkyl-9-aminomethyltriptycenes. Participation of a neighboring 1-alkyl substituent

      Gaku Yamamoto, Ai Koseki, Jun Sugita, Hisashi Mochida, Mao Minoura

      Bulletin of the Chemical Society of Japan79 ( 10 ) 1585 - 1600   2006年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Deamination reactions of 1-alkyl-9-aminomethyltriptycenes (alkyl = Me, Et, i-Pr, and t-Bu) and 9-(1-aminoethyl)-1-methyltriptycene were performed in CHCl 3 and in AcOH, and product distributions were studied. The results suggest that the loss of N 2 from a primary alkanediazonium ion predominantly takes place concomitantly with participation of a C-H bond of the neighboring 1-alkyl group to form a nonclassical cationic species with a three-center two-electron bonding, while the loss of N 2 from a secondary alkanediazonium ion occurs spontaneously to form a secondary carbocation. Solvent effects (CHCl 3 vs AcOH) are explained in terms of lower nucleophilicity/basicity of the AcO - in AcOH than in CHCl 3 due to solvation. © 2006 The Chemical Society of Japan.

      DOI: 10.1246/bcsj.79.1585

      Scopus

      researchmap

    • Synthesis and structures of 9-triptycylallene derivatives

      Gaku Yamamoto, Yuriko Kobayashi, Kasumi Ono, Emiko Yano, Mao Minoura, Yasuhiro Mazaki

      Bulletin of the Chemical Society of Japan79 ( 8 ) 1293 - 1299   2006年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      9-Triptycylallene (1) was synthesized by LiAlH 4 reduction of 1-(9-triptycyl)-2-propynyl methanesulfonate (7), and three 3-substituted derivatives of 1 were also obtained by reacting compound 7 with appropriate metal reagents. LiAlH 4 reduction of 1,3-di(9-triptycyl)-2-propynyl methanesulfonate (10) gave 1,3-di(9-triptycyl)propyne (12). The molecular structures of some of the allenes and of the propyne were determined by X-ray crystallography. As well, the allenes and some of the related compounds were characterized by NMR spectroscopy. © 2006 The Chemical Society of Japan.

      DOI: 10.1246/bcsj.79.1293

      Scopus

      researchmap

    • Static and dynamic stereochemistry of tris(9-triptycyl)stannane derivatives

      Gaku Yamamoto, Shozo Ohta, Megumi Kaneko, Kaoru Mouri, Miki Ohkuma, Ryo Mikami, Yosuke Uchiyama, Mao Minoura

      Bulletin of the Chemical Society of Japan78 ( 3 ) 487 - 497   2005年3月15日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Static and dynamic stereochemistry of several tris(9-triptycyl)stannane derivatives Tp3SnX (X = H, halogens, and alkyl groups) were studied. X-ray crystallography of the bromo and methyl compounds showed that the Sn atom was fundamentally tetrahedral and that the three Tp groups meshed with each other like bevel gears and formed a near-C3 chiral conformation. The rate constants for enantiomerization of the chiral conformation in solution could be obtained by the lineshape analysis of the aromatic proton signals, even when a direct probe for enantiomerization such as a benzyl group was absent. The energy barrier to enantiomerization decreased as the substituent X became bulkier, suggesting that the ground state is more destabilized than the transition state upon introduction of a bulkier group. © 2005 The Chemical Society of Japan.

      DOI: 10.1246/bcsj.78.487

      Scopus

      researchmap

    • Open-cage fullerene derivatives suitable for the encapsulation of a hydrogen molecule

      Shigeru Nagase, Iwamatsu S, Nagase S, Naomi Mizorogi, Kobayashi K, Yukihiro Andoh, Shizuaki Murata, Sho-ichi Iwamatsu, Mao Minoura

      The Journal of Organic Chemistry   2005年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1021/JO050251W

      researchmap

    • Synthesis and characterization of stable hypervalent carbon compounds (10-C-5) bearing a 2,6-bis(p-substituted phenyloxymethyl)benzene ligand 査読有り 国際誌

      Akiba KY, Moriyama Y, Mizozoe M, Inohara H, Nishii T, Yamamoto Y, Minoura M, Hashizume D, Iwasaki F, Takagi N, Ishimura K, Nagase S

      Journal of the American Chemical Society127 ( 16 ) 5893 - 5901   2005年

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      DOI: 10.1021/ja043802t

      Scopus

      PubMed

      researchmap

    • Syntheses and reactions of hexavalent organotellurium compounds bearing five or six tellurium-carbon bonds 国際誌

      Masataka Miyasato, Takao Sagami, Mao Minoura, Yohsuke Yamamoto, Kin Ya Akiba

      Chemistry - A European Journal10 ( 10 ) 2590 - 2600   2004年5月17日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A variety of hexaorganotellurium compounds, Ar6-n(CH 3)nTe [Ar = 4-CF3C6H4, n = 0 (1a), n = 1 (3a), n = 2 (trans-4a and cis-4a), n = 3 (mer-5a), n = 4 (trans-6a); Ph, n = 0 (1b), n = 1 (3b), n = 2 (trans-4b); 4-CH3C 6H4, n = 0 (1c), n = 1 (3c), n = 2 (trans-4c), n = 4 (trans-6c); 4-BrC6H4, n = 0 (1d)] and Ar5(R)Te [Ar = 4-CF3C6H4, R = 4-CH3OC 6H4 (8); Ar = 4-CF3C6H4, R = vinyl (9), Ar = Ph, R = vinyl (10), Ar = 4-CF3C6H 4, R = PhSCH2 (11), Ar = Ph, R = PhSCH2 (12), Ar = 4-CF3C6H4, R = nBu (13)] and pentaorganotellurium halides, Ar5TeX [Ar = 4-CF3C 6H4, X = Cl (2a-Cl), X = Br (2a-Br); Ar = Ph, X = Cl (2b-Cl), X = Br (Zb-Br); Ar = 4-CH3C6H4, X = Cl (2c-Cl), X = Br (2c-Br); Ar = 4-BrC6H4, X = Br (2d-Br)] and (4-CF3C6H4)4(CH3)TeX [X = Cl (trans-7a-Cl) and X = Br (trans-7a-Br)] were synthesized by the following methods: 1) one-pot synthesis of 1a, 2) the reaction of SO 2Cl2 or Br2 with Ar5Te Li + generated from TeCl4 or TeBr4 with five equivalents of ArLi, 3) reductive cleavage of Ar6-m(CH 3)mTe (m = 0 or 2) with KC8 followed by treatment with CH3I, 4) valence expansion reaction from low-valent tellurium compounds by treatment with KC8 followed by reaction with CH3I, 5) nucleophilic substitution of Ar6-y-z(CH 3)zTeXy-z (X=Cl, Br, OTf; z = 0, 1; y= 1, 2) with organolithium reagents. The scope and limitations and some details for each method are discussed and electrophilic halogenation of the hexaorganotellurium compounds is also described.

      DOI: 10.1002/chem.200305260

      Scopus

      PubMed

      researchmap

    • Synthesis and stereochemistry of N-phenyl-N-9-triptycylhydroxylamine derivatives and related compounds

      Chiharu Agawa, Keiko Otsuka, Mao Minoura, Yasuhiro Mazaki, Gaku Yamamoto

      Bulletin of the Chemical Society of Japan77 ( 12 ) 2273 - 2281   2004年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      During the course of attempts at synthesis of N-phenyl-N-9- triptycylhydroxylamine (1), we found that the reaction of N-9- triptycylhydroxylamine (5) with benzenediazonium-2-carboxylate afforded 3-(2-carboxyphenyl)-1-(9-triptycyl)-triazene 1-oxide (6), the structure of which was confirmed by X-ray crystallography. Oxidation of N-(9-triptycyl)aniline (4) with mCPBA gave phenyl 9-triptycyl nitroxide (7) and N-(9-triptycyl)-1,4- benzoquinonimine (8) in small yields. Reduction of 7 with phenylhydrazine gave 1, and O-ethylation of 1 gave O-ethyl-N-phenyl-N-9-triptycylhydroxylamine (2). Results of X-ray crystallography for compounds 2, 4, 7, and 8 and results of dynamic NMR studies for 1, 2, and 8 are presented. In compound 8, Tp-N rotation and C=N topomerization took place on the NMR timescale at high temperatures above 60 °C, and the energy barriers to both processes were obtained. In compounds 1 and 2. dynamic NMR behavior was observed at very low temperatures below ca. -50 °C, and the energy barriers to the respective processes could not be determined except for those related to "Ph-passing".

      DOI: 10.1246/bcsj.77.2273

      Scopus

      researchmap

    • Dynamic Stereochemistry of Alkyltris(9-triptycyl)stannanes

      Gaku Yamamoto, Megumi Kaneko, Miki Ohkuma, Mao Minoura

      Chemistry Letters32 ( 10 ) 964 - 965   2003年10月5日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      1H dynamic NMR study of benzyltris(9-triptycyl)stannane (4) using two probes, the benzylic methylene and the aromatic peri-proton signals, revealed that the enantiomerization of the chiral conformers took place with ΔG‡ of 64.2 kJ mol-1 at 300 K.

      DOI: 10.1246/cl.2003.964

      Scopus

      researchmap

    • Static and dynamic stereochemistry of O-substituted N-9-triptycylhydroxylamines

      Gaku Yamamoto, Chiharu Agawa, Mao Minoura

      Bulletin of the Chemical Society of Japan76 ( 4 ) 825 - 829   2003年4月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The static and dynamic stereochemistry of N-9-triptycylhydroxylamine derivatives (TpNHOR) with O-benzyl (3), O-ethyl (4), and O-phenyl (5) groups were studied. X-ray crystallographic analysis revealed that these compounds reside in a chiral conformation, with the Tp-N-O-R dihedral angle of 140-160°. Dynamic NMR studies of 3 and 4 show the presence of two separate stereomutation processes: chirality reversal (enantiomer interconversion) and rotation of the Tp-N bond with retaining the chirality, the latter having a lower energy barrier. Compound 5 gave solely information on the Tp-N rotation because of the lack of a probe for chirality reversal.

      DOI: 10.1246/bcsj.76.825

      Scopus

      researchmap

    • Static and dynamic stereochemistry of N-(1,4-dimethyl-9-triptycyl)-hydroxylamine derivatives

      Gaku Yamamoto, Chiharu Agawa, Takahiro Ohno, Mao Minoura, Yasuhiro Mazaki

      Bulletin of the Chemical Society of Japan76 ( 9 ) 1801 - 1811   2003年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Static and dynamic stereochemistry of N-alkyl, O-alkyl, and N,O-dialkyl derivatives of N-(1,4-dimethyl-9-triptycyl)hydroxylamine were studied. X-ray crystallographic analysis revealed that an N-alkyl derivative adopts R*-(-sc)* conformation while N,O-dialkyl derivatives adopt R*-ap conformation. In solufion, stereomutation was almost frozen on the NMR timescale at ca. -60 °C. The same conformer as found in the crystal was the major conformer in solution in each compound, and a small amount of a second conformer was found in equilibrium with the major one for the N-alkyl and N,O-dialkyl derivatives. The stereomutation was interpreted in terms of diastereomerization and enantiomerization, and the 1H NMR lineshape analysis afforded the activation parameters for these processes.

      DOI: 10.1246/bcsj.76.1801

      Scopus

      researchmap

    • Novel Valence Expansion Reactions Using KC_8 : A New Route to Hexavalent Organotellurium Compounds from Divalent Tellurium

      MIYASATO Masataka, MINOURA Mao, YAMAMOTO Yohsuke, AKIBA Kin-ya

      Chemistry letters2002 ( 3 ) 288 - 289   2002年3月5日

      詳細を見る

      掲載種別:研究論文(学術雑誌)   出版者・発行元:The Chemical Society of Japan  

      Hexavalent tellurium compounds, Ar&lt;SUB&gt;5&lt;/SUB&gt;(CH&lt;SUB&gt;3&lt;/SUB&gt;)Te, Ar&lt;SUB&gt;4&lt;/SUB&gt;(CH&lt;SUB&gt;3&lt;/SUB&gt;)&lt;SUB&gt;2&lt;/SUB&gt;Te, and Ar&lt;SUB&gt;2&lt;/SUB&gt;(CH&lt;SUB&gt;3&lt;/SUB&gt;)&lt;SUB&gt;4&lt;/SUB&gt;Te (Ar=4-CF&lt;SUB&gt;3&lt;/SUB&gt;C&lt;SUB&gt;6&lt;/SUB&gt;H&lt;SUB&gt;4&lt;/SUB&gt;, Ph, 4-CH&lt;SUB&gt;3&lt;/SUB&gt;C&lt;SUB&gt;6&lt;/SUB&gt;H&lt;SUB&gt;4&lt;/SUB&gt;), were synthesized by the reaction of Ar&lt;SUB&gt;2-n&lt;/SUB&gt;(CH&lt;SUB&gt;3&lt;/SUB&gt;)&lt;SUB&gt;n&lt;/SUB&gt;Te (n=0–1) or Ar&lt;SUB&gt;3-m&lt;/SUB&gt;(CH&lt;SUB&gt;3&lt;/SUB&gt;)&lt;SUB&gt;m&lt;/SUB&gt;Te&lt;SUP&gt;+&lt;/SUP&gt;X&lt;SUP&gt;-&lt;/SUP&gt; (m=0–2) with KC&lt;SUB&gt;8&lt;/SUB&gt; followed by the treatment with CH&lt;SUB&gt;3&lt;/SUB&gt;I.

      DOI: 10.1246/cl.2002.288

      Scopus

      CiNii Article

      researchmap

    • Studies on tellurium-containing heterocycles. Part 18. Preparation and structure of 2-benzotelluropyrylium salts and 2-benzoselenopyrylium salts

      Haruki Sashida, Kazuo Ohyanagi, Mao Minoura, Kin Ya Akiba

      Journal of the Chemical Society. Perkin Transactions 12 ( 5 ) 606 - 612   2002年2月22日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The regioselective and stereospecific intramolecular ring closure reactions of o-ethynylbenzyl tellurols 5A and o-ethynylbenzyl selenols 5B, which were readily generated by the reaction of the o-ethynylbenzyl bromides 4 with sodium hydrogen telluride (NaHTe) or sodium hydrogen selenide (NaHSe), produced the isotellurochromenes 6A and isoselenochromenes 6B together with (Z)-1-methylidene-2-telluraindans 7A and (Z)-1-methylidene-2-selenaindans 7B, respectively. The obtained isochromenes 6A and 6B were transformed into the corresponding 2-benzotelluropyrylium tetrafluoroborates 9A and 2-benzoselenopyrylium tetrafluoroborates 9B by treatment with triphenylcarbenium tetrafluoroborate (Ph3C+BF4 −) in excellent yields, respectively. An X-ray structural analysis of the tert-butyl derivatives 9Ac and 9Bc is also described. © 2002 The Royal Society of Chemistry.

      DOI: 10.1039/b111045b

      Scopus

      researchmap

    • Coordination of trimethylphosphine with pentaphenyltelluronium salts

      Masataka Miyasato, Takahiro Mukuda, Mao Minoura, Yohsuke Yamamoto, Kin Ya Akiba

      Phosphorus, Sulfur and Silicon and Related Elements177 ( 8-9 ) 2043 - 2044   2002年

      詳細を見る

      掲載種別:研究論文(国際会議プロシーディングス)  

      DOI: 10.1080/10426500213441

      Scopus

      researchmap

    • Cleavage of tellurium - Carbon bonds of hexavalent organotellurium compounds by potassium graphite 国際誌

      Masataka Miyasato, Mao Minoura, Kin Ya Akiba

      Angewandte Chemie - International Edition40 ( 14 ) 2674 - 2676   2001年7月16日

      詳細を見る

      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      The potassium ion intercalated in graphite results in unique reactivity of Ar5Te-K+C8 (1), formed by cleavage of one of the Te-C(Ar) bonds of Ar6Te (see scheme) by KC8. Thus, 1 reacted quantitatively with CH3I to give Ar5TeCH3, which was not obtainable from Ar5Te-Li+. The Te-CH3 bond of Ar5TeCH3 is cleaved in preference to the Te-C(Ar) bonds, and formation of Ar4Te(CD3)2 suggests the intermediacy of the hypervalent dianion Ar4Te2-.

      DOI: 10.1002/1521-3773(20010716)40:14<2674::AID-ANIE2674>3.0.CO;2-H

      Scopus

      PubMed

      researchmap

    • Convenient one-pot synthesis and structures of pentaphenyltellurium monohalides

      Mao Minoura, Takao Sagami, Kin Ya Akiba

      Organometallics20 ( 12 ) 2437 - 2439   2001年6月11日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      A novel family of organochalcogens, Ph5TeX (X = Cl, Br), was readily obtained by the halogenation of Ph5TeLi, which was prepared by reaction of 5 equiv of PhLi with 1 equiv of TeCl4 or TeBr4; Ph5TeF was obtained by treating the bromide with KF. The Te atom is in the highest oxidation state, Te(VI), and is covalently bonded to the halogen atom, in contrast to the ionic bonding in R3TeIVX.

      DOI: 10.1021/om001075e

      Scopus

      researchmap

    • Synthesis and structure of pentaphenyl-telluronium salts of perchlorate and tetrakis{3,5-bis(trifluoromethyl)phenyl}borate: hypervalent onium compounds

      Mao Minoura, Takahiro Mukuda, Takao Sagami, Kin Ya Akiba

      Heteroatom Chemistry12 ( 5 ) 380 - 384   2001年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The reaction of pentaphenyltellurium chloride 2 with silver perchlorate afforded the pentaphenyltelluronium salt, Ph5Te+ClO4-, (1b), and treatment of 2 with silver triflate and sodium tetrakis{3,5-bis(trifluoromethyl)phenyl}borate provided Ph5Te+[3,5-(CF3)2C6H 3]4B- (1c), which were isolated as stable yellow solids. X-ray crystallographic analysis of the hypervalent telluronium salts revealed square pyramidal geometry around the tellurium, which are rare examples for penta-substituted main group element compounds.

      DOI: 10.1002/hc.1057

      Scopus

      researchmap

    • Synthesis and characterization of a hypervalent tellurium cation, Ph<inf>5</inf>Te<sup>+</sup>: A stable nonclassical onium compound [13]

      Mao Minoura, Takahiro Mukuda, Takao Sagami, Kin Ya Akiba

      Journal of the American Chemical Society121 ( 46 ) 10852 - 10853   1999年11月24日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1021/ja992828v

      Scopus

      researchmap

    • Structure of azabismocines, hexacoordinate pentavalent organobismuth compounds

      Mao Minoura, Yuka Kanamori, Akira Miyake, Kin Ya Akiba

      Chemistry Letters ( 9 ) 861 - 862   1999年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Azabisomocine derivatives having a pentavalent bismuth and a nitrogen at 1,5-position were synthesized. The X-ray structural analysis reveals that these compounds have hexacoordinate distorted octahedral geometry which is caused by transannular bond formation between the bismuth and the nitrogen.

      DOI: 10.1246/cl.1999.861

      Scopus

      researchmap

    • Stable Telluroketones: Synthesis and Characterization 査読有り

      Mao Minoura, Takayuki Kawashima, Norihiro Tokitoh, Renji Okazaki

      Phosphorus, Sulfur, and Silicon and the Related Elements136 ( 1 ) 549 - 552   1998年1月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)   出版者・発行元:Informa UK Limited  

      DOI: 10.1080/10426509808545993

      Scopus

      researchmap

    • Synthesis and characterization of hexaaryltellurium (TeAr<inf>6</inf>); The first neutral hexaarylated element compound

      Mao Minoura, Takao Sagami, Masataka Miyasato, Kin Ya Akiba

      Tetrahedron53 ( 36 ) 12195 - 12202   1997年9月8日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Te(C6H4-CF3)6 1a was obtained by the unique one-pot reaction of LiC6H4-4-CF3 with TeCl4. The Te atom resides in the highest oxidation state (Te(VI)) having six C-Te bonds in 1a. Compound la is extremely thermally stable and not light sensitive unlike tetraorganotellurium compounds. The X-ray crystallographic analysis of 1a revealed a rare example of approximately T(h) molecular symmetry.

      DOI: 10.1016/S0040-4020(97)00552-8

      Scopus

      researchmap

    • Δ-1,3,4-Telluradiazolines, a novel tellurium containing heterocycle: One-pot synthesis, structure, and reactivity

      Mao Minoura, Takayuki Kawashima, Norihiro Tokitoh, Renji Okazaki

      Tetrahedron53 ( 24 ) 8137 - 8148   1997年6月16日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The one-pot reaction of sterically hindered hydrazones with tellurium dichloride or tellurium tetrahalide in the presence of triethylamine in benzene afforded Δ3-1,3,4-telluradiazolines 1, a novel heterocycle, via 1,3-dipolar cycloaddition of telluroketones and diazo compounds, both generated in situ. The molecular structure of 1a was established by X-ray crystallographic analysis. The photolysis of In led to instant and quantitative formation of the corresponding azine 8a, whereas the thermolysis of in in the solid state afforded the corresponding retrocyclization products.

      DOI: 10.1016/S0040-4020(97)00498-5

      Scopus

      researchmap

    • The first isolation of a telluroketone and its reversible dimerization

      Mao Minoura, Takayuki Kawashima, Renji Okazaki

      Tetrahedron Letters38 ( 14 ) 2501 - 2504   1997年4月

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      The solid-state thermolysis of a sterically hindered Δ3-1,3,4-telluradiazoline 2 afforded products resulting from intermediary tellone 1 and diazo compound 8 formed by retrocyclization, whereas the flash vacuum thermolysis of 2 led to isolation of tellone 1 as green needles. The spontaneous dimerization of 1 thus obtained occurred in the solid state to give the corresponding 1,3-ditelluretane 10, which underwent the thermal cycloreversion in solution to regenerate pure tellone 1.

      DOI: 10.1016/S0040-4039(97)00377-8

      Scopus

      researchmap

    • Weak coordination of a telluroketone in an η<sup>1</sup>-mode complex: Synthesis and characterization of pentacarbonyl(1,1,3,3-tetramethylindantellone)tungsten

      Mao Minoura, Takayuki Kawashima, Norihiro Tokitoh, Renji Okazaki

      Chemical Communications ( 2 ) 123 - 124   1996年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      Treatment of a stable telluroketone with W(CO)5·thf affords the title compound, the X-ray crystal structure of which shows η1,σ-complexation and the trans influence of the weakly coordinated telluroketone; the regeneration of a 'free' telluroketone by ligand exchange of the complex under mild conditions is also reported.

      DOI: 10.1039/CC9960000123

      Scopus

      researchmap

    • Hexaaryltellurium

      Mao Minoura, Takao Sagami, Kin Ya Akiba, Claudia Modrakowski, Allexander Sudau, Konrad Seppelt, Stephan Wallenhauer

      Angewandte Chemie (International Edition in English)35 ( 22 ) 2660 - 2662   1996年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1002/anie.199626601

      Scopus

      researchmap

    • Stable Telluroketones and Their Related Compounds: Synthesis, Structure, and Reactivity 査読有り

      Mao MINOURA

          1995年3月30日

      詳細を見る

      記述言語:英語   掲載種別:学位論文(博士)  

      researchmap

    • Tropothione <i>S</i> -Sulfide. A New Class of Thiosulfine

      Mao Minoura, Shinichi Yamabe, Takahisa Machiguchi, Taketoshi Minato

      Chemistry Letters   1995年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1246/CL.1995.103

      researchmap

    • Synthesis structure, and reactivity of 1,4,2-oxa-tellurazole: A novel tellurium-containing heterocycle

      Mao Minoura, T. Takayukikawashima, Renji Okazaki

      Phosphorus, Sulfur, and Silicon and the Related Elements93 ( 1-4 ) 403 - 404   1994年8月1日

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      A novel tellurium containing heterocycle, 1,4,2-oxatellurazole, was characterized by X-ray crystallographic analysis which showed a remarkably small C-Te-C bond angle (79.4°), and its 1,3-dipolar cycloreversion is discussed. © 1994, Taylor & Francis Group, LLC. All rights reserved.

      DOI: 10.1080/10426509408021877

      Scopus

      researchmap

    • STRUCTURE AND THERMOLYSIS OF A 1,4,2-OXATELLURAZOLE, A NOVEL TELLURIUM CONTAINING HETEROCYCLE

      Renji Okazaki, Takayuki Kawashima, Mao Minoura

      Chemistry Letters   1994年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1246/CL.1994.1691

      researchmap

    • SYNTHESIS OF DELTA-3-1,3,4-TELLURADIAZOLINES, A NOVEL TELLURIUM-CONTAINING HETEROCYCLE

      Takayuki Kawashima, Renji Okazaki, Mao Minoura

      Chemistry Letters   1993年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1246/CL.1993.1047

      researchmap

    • 1,1,3,3-Tetramethylindantellone, the first telluroketone stable in solution

      Mao Minoura, Takayuki Kawashima, Renji Okazaki

      Journal of the American Chemical Society115 ( 15 ) 7025 - 7026   1993年

      詳細を見る

      掲載種別:研究論文(学術雑誌)  

      DOI: 10.1021/ja00068a088

      Scopus

      researchmap

    ▼全件表示

    MISC

    書籍等出版物

    • ラウドン有機化学

      Loudon, G. Marc, Parise, Jim, 後藤, 敬, 豊田, 真司, 箕浦, 真生, 村田, 滋, 山本, 学

      東京化学同人  2018年  ( ISBN:9784807909438

      詳細を見る

      総ページ数:2冊   記述言語:日本語

      CiNii Books

      researchmap

    • 有機化学

      奥山 格, 石井昭彦, 箕浦真生( 担当: 共著)

      丸善出版  2016年1月29日  ( ISBN:4621089773

      詳細を見る

      記述言語:日本語 著書種別:教科書・概説・概論

      researchmap

    所属学協会

    ▼全件表示

    共同研究・競争的資金等の研究

    • ジシレンジアニオン種を鍵分子とする未踏典型元素共役系分子の創製

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      箕浦 真生

      詳細を見る

      2022年4月 - 2025年3月

      課題番号:22K05085

      配分額:4290000円 ( 直接経費:3300000円 、 間接経費:990000円 )

      researchmap

    • 高周期典型元素π電子をもつ未踏高反応性化学種の創製

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      箕浦 真生

      詳細を見る

      2019年4月 - 2022年3月

      課題番号:19K05425

      配分額:4290000円 ( 直接経費:3300000円 、 間接経費:990000円 )

      本研究課題では、高周期典型元素を含むπ電子の特性を理解するために、トリプチシル骨格を基盤とする汎用性の高いアルキル立体保護基を新たに開発し、高反応性π結合に十分な速度論的安定化を与え、第2周期元素の化学を高周期元素へ展開し、互変異性可能な高周期元素ケトン類縁体(R2E=Ch,E = Si, Ge, Sn, Pb; Ch = O, S, Se, Te)、および新規高周期典型元素不飽和結合をもつ化学種の創製を行い、基本的π結合の性質解明を目的とする。 構築した新規化学結合周辺部の反応空間を併せもつ高周期アルケン、アルキン、カルベンおよびアゾ化合物同族体を創出し、これら高反応性典型元素化学種を用いる小分子活性化を検討する他、これまで未解明であった典型元素π電子・π結合の特性解明を行い、 元素化学の学理構築に繋げ、学術的知的再生産を行うことを目的としている。
      これまでに、有用と考えられる嵩高いアルキル置換基(Trp*)を開発し、高周期カルベン同族体であるTrp*2Ge:およびTrp*Sn:を安定な化合物として単離しており、それらの更なる誘導化による高周期元素ケトン類縁体の合成単離にも成功している。アルキン同族体であるTrp*2Si2やそのジアニオン種に相当する[Trp*2Si2]K2や対応するゲルマニウム化合物についても合成単離することが出来、これまでに未知であった新しいπ電子豊富な化学結合を含む化学種を得ている。また、これらの反応性を検討すると共に結晶構造解析にも成功した。

      researchmap

    • 互変異性化可能な高周期典型元素不飽和化合物の創製

      日本学術振興会  科学研究費助成事業 

      箕浦真生

      詳細を見る

      2015年4月 - 2018年3月

      課題番号:15K05439

      担当区分:研究代表者  資金種別:競争的資金

      互変異性化可能な高周期ケトン類縁体に必須となるα位に水素を有する嵩高い置換基を設計開発し、その合成と高周期元素の導入を行った。トリプチシル(Trp)骨格を拡張し、かつメチレン基を有する嵩高いTrp*CH2基を新規アルキル立体保護基として用い、α位に水素を有するケイ素―硫黄二重結合化学種であるシランチオン、ならびに中間体として得られるシリレンの合成検討を行った。嵩高いTrp*CH2とTrp基を用いることで、溶液中安定なシランチオンおよび熱的に極めて安定なジシレンに誘導することに成功した。ケイ素上に導入したTrp*CH2とTrp基の噛み合いによる新しい立体保護効果の発現といえる。

      researchmap

    • 多様な酸化状態を有する高周期16族元素感応性化学種の創製と反応

      文部科学省  科学研究費助成事業 

      箕浦真生

      詳細を見る

      2015年4月 - 2017年3月

      課題番号:15H00962

      担当区分:研究代表者  資金種別:競争的資金

      含高周期カルコゲン(Te, Se, S)有機化合物には、酸素がもたない種々の酸化状態の変化に伴う多様性があり、興味が持たれているにも関わらず、化合物の合成的困難さのため、基本的性質が不明であり、十分な研究が行われていない。
      本課題は、高反応(不安定)性のため、合成が避けられていたカルコゲン化合物群の創製を行うものであり、酸素がもたない種々の酸化状態の変化に伴う多様性と感応性を解明することを目的とする。
      「感応性超原子価4および6価カルコゲン化合物」:第五周期元素であるテルルを中心元素とする四価中性有機テルル(Ar4Te)の酸化的ハロゲン化とその脱ハロゲン化により六価有機テルルジカチオン(Ar4Te2+)の一般的合成法とその官能基化手法を確立した。ジカチオン種を用いることで多様な中性六価有機テルル化合物へ誘導可能となった。
      「感応性2価カルコゲン化合物」:剛直な骨格を有するトリプチシル基の周縁領域をアルキル基により拡張した新規立体保護基を開発・活用し、橋頭位に硫黄、セレン、テルルをそれぞれ導入し、対応するスルフェン酸、セレネン酸、テルレン酸の合成検討を行った。テルルの場合は分解反応を抑制できなかったが、硫黄・セレンの場合には熱的に安定な二価化学種を合成単離することが出来た。

      researchmap

    • 高周期14族元素カチオン種の発生と小分子活性化に基づく複素環化合物の創製

      日本学術振興会  科学研究費助成事業 

      川島隆幸

      詳細を見る

      2014年4月 - 2017年3月

      課題番号:26410035

      資金種別:競争的資金

      芳香環を有するヒドロシランからトリチルカチオンにより発生させたシリルカチオンと、アルキン、アルケンや二酸化炭素などから生じたカルボカチオン種を、芳香環へ反応させ、対応する含ケイ素環状化合物を合成した。また、隣接位にアルキニル基とヒドロシリル基を1または2組有する芳香族化合物へ適用し、ベンゾシロール、ナフトシロール,ジシロール類などのπ-拡張シロールを合成した。さらに、ゲルマ-Friedel-Crafts反応を開発し、ジベンゾゲルモールの合成に成功した。

      researchmap

    • 種々の酸化状態を有する高周期カルコゲン感応性化学種の創製と反応

      日本学術振興会  科学研究費助成事業 新学術領域研究(研究領域提案型) 

      箕浦 真生

      詳細を見る

      2013年4月 - 2015年3月

      課題番号:25109541

      配分額:7280000円 ( 直接経費:5600000円 、 間接経費:1680000円 )

      本課題は、高反応(不安定)性のため、合成が避けられていた感応性カルコゲン化合物群の創製を行うものであり、酸素がもたない種々の酸化状態の変化に伴う多様性を解明することを目的とし、とりわけ合成が困難とされている電子供与性置換基を有する4および6価の高酸化状態をもつ「感応性超原子価カルコゲン化合物」の創製と反応を行うことを中心課題として研究を行った。
      「感応性超原子価カルコゲン化合物」:ジメチルアミノフェニル(Ar)基を電子供与性置換基として選び、中性4価テトラアリールテルル(Ar4Te)の合成検討を行った。各種合成条件を検討し、純粋なアリールリチウムを単離し供することで、中性4価テトラアリールテルルの合成単離に成功した。酸素・水等により容易に分解し、また微量の不純物の混入が分解を促進することも明らかとなった。合成単離したAr4Teは熱的にも高反応性であり、加熱により還元的脱離反応をおこし、定量的にAr2TeとAr2を与える事が明らかとなった。
      対応する6価テトラアリールテルルジフルオリドへもXeF2による酸化的ハロゲン化により導くことが出来た。結晶構造解析により、固体中ではテルルを中心とするオクタヘドラル構造を有している。芳香族置換基のパラ位に各種置換基を導入したAr*4TeF2を合成・比較したところ、電子供与性効果が大きいほど長く弱いTe-F結合となることが認められた。
      等電子構造を有する超原子価アンチモン化合物であるAr**5Sbを合成し、Ar*4Teとの混合条件下では、配位子交換反応が速やかにおこり、続く還元的脱離が進行することを実験的に初めて証明することが出来た。この交換反応は超原子価感応性化学種が高反応性を示す要因の一つと見なすことが出来ると考えられる。

      researchmap

    • 弱い化学結合をもつ未踏16族元素化合物の創製

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      箕浦 真生

      詳細を見る

      2012年4月 - 2015年3月

      課題番号:24550063

      配分額:5590000円 ( 直接経費:4300000円 、 間接経費:1290000円 )

      高周期典型元素化合物の化学は、弱い多重結合(パイ結合)に嵩高い置換基を導入して速度論的安定化による手法により発展してきた。しかし、高周期元素を含む弱いシグマ結合の性質解明はその不安定性のため充分に行われていない。本研究では、とりわけ弱いシグマ結合をもつことで知られる高周期16族元素未踏分子群の創製を行い、それらの性質解明を目的とした。高純度試薬を調製し不安定中間体を単離することで、1)高周期16-14族元素間単結合をもつテルリド類の系統的合成と単離、2)高度に分極したイミダゾリウムカルコゲノラートの合成法の開発、3)過酸化物の酸素を高周期元素に置き換えた不飽和スルフェン酸の合成を達成した。

      researchmap

    • イソセレノシアナートおよび関連化合物を用いる有用カルコゲン含有複素環合成

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      指田 春喜, 要 衛, 箕浦 真生

      詳細を見る

      2011年 - 2013年

      課題番号:23590023

      配分額:5460000円 ( 直接経費:4200000円 、 間接経費:1260000円 )

      分子内に三重結合,あるいは適当な脱離基を有する各種求核剤とイソセレノシアナート類(関連化合物)の環化付加反応,およびその逆の組み合わせである三重結合(脱離基)を有するイソセレノシアナート類と各種種求核剤の環化付加反応,この2種の反応を駆使することにより,簡便かつ効率的にカルコゲン(セレン,テルル,硫黄)原子を含む新規な複素環化合物の創成を行った。また,得られた化合物の構造・反応性などその化学の解明を行った。環化反応として,ヨウ素環化を行うことにより,さらに官能基化された生成物がえられた。複素環合成を目的とした新規なジカルコゲニド類のヨウ素環化反応を見出した。

      researchmap

    • 炭素配位子のみからなる新規4および6価有機16族元素化合物の創製と性質の解明

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      箕浦 真生

      詳細を見る

      2008年 - 2010年

      課題番号:20550050

      配分額:4940000円 ( 直接経費:3800000円 、 間接経費:1140000円 )

      通常は不安定であると考えられていた電子供与性置換基をもつ超原子価4価テルル化合物の合成単離に成功し、4本の化学結合を持つ分子で、初めて基底状態で四角錐構造を有することを明らかにした。また、電子供与性ジメチルアミノフェニル基を持つテルロニウム塩が、高周期16族元素オニウムとして緑青色を示すことを発見し、機能性色素分子として性質を明らかにした。さらに6 価テルル化合物の置換基上での官能基導入変換方法を確立し、機能性官能基を導入可能な、重要な出発原料となる一連の典型元素オクタヘドラル化合物群の合成単離に成功した。

      researchmap

    • 安定な超原子価有機テルルアニオン種の創製とそれらの中性オクタヘドラル分子への変換

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      箕浦 真生

      詳細を見る

      2006年 - 2007年

      課題番号:18550045

      配分額:4190000円 ( 直接経費:3800000円 、 間接経費:390000円 )

      5本の化学結合を一つの元素上に有するアニオン性化学種は、アート錯体と呼ばれ重要な反応中間体として知られているが、一般に不安定であり反応性や構造は未解明であった。研究代表者は中心元素にテルルを選び、これまで未知である超原子価有機テルルアニオン種R_5Te^-を合成単離し、その性質を明らかにすることを目的として研究を行った。その結果、初めての超原子価16族元素アニオン種として、Ph_5Te^-Li^+を合成し、低温下黄色結晶として単離し、その分子構造を低温結晶構造解析により明らかにすることに成功した。超原子価アニオン種はテルル中心で四角錐構造(擬オクタヘドラル)を有しており、これまでに観測された炭素-テルル結合のうちでもっとも長い値を示した。この超原子価化アニオン種には溶液中で速やかな解離平衡が存在するものの、-100℃では安定に存在することが明らかとなった。
      テルル上の求電子試剤による官能基化を検討し、ヨウ化メチルやハロゲン等の求電子試薬との反応では、対応するオクタヘドラル構造を有する安定な中性6価有機テルル化合物群へ変換出来た。また上記研究課題の遂行途中で4-メトキシフェニル基を有するテトラアリールテルルが固体中で擬四角錐構造を有することを発見し、今後の研究の端緒も得た。
      本研究で得られた新規な知見は、16族元素のみならず他の高周期元素アニオン種へも適応可能であり、アニオン性新規化合物群の合成と性質の理解へと拡張する上で意義深いものと考えている。

      researchmap

    • 新規スタンニル基を立体保護基とする新しい典型元素化合物の創製

      日本学術振興会  科学研究費助成事業 基盤研究(C) 

      箕浦 真生

      詳細を見る

      2004年 - 2005年

      課題番号:16550043

      配分額:3700000円 ( 直接経費:3700000円 )

      第三周期以降の典型元素化合物の研究において、嵩高い置換基を導入し速度論的に安定化された種々の典型元素化合物が合成され、近年注目を集めている。我々は電気陽性なスズを中心官能基化元素に選び、剛直なトリプチセン(Trp)骨格を3つ有するトリス(9-トリプチシル)スタンニル基(Trp3Sn-)を新しい立体保護基として用いる検討を行ってきた。これまでに、スズ上に典型元素官能基の導入検討を行い、初めての安定なスタンナンチオールやアシルスタンナンなどの合成単離等が可能となった。
      チオール体の酸化反応により対応するスタンナンスルフェン酸(Trp3Sn-SOH)の合成に成功し、その結晶構造を明らかにし、このスルフェン酸の熱分解反応における速度論的検討から、Sn-S-Oの3員環を含む超原子価遷移状態を経由して対応するアルコール体を定量的に与えることを見いだした。
      一方で、この置換基のスズ原子上に導入した官能基の変換反応は、新しい官能基の性質を知る上で重要であるが、立体障害のため困難であった。例えぼ、合成したアシルスタンナン類と有機リチウム試薬との反応では、スズ上でのアート型錯体形成と続くアシルリチウムの発生を確認できたものの、カルボニル炭素上は求核試剤との反応性を示さなかった。また、Trp3Sn-基を複数個典型元素上に導入する検討は困難であったため、スズを官能基導入元素とする新たな立体保護基の開発に着手した。3つのTrp基の一つをメチル基に置き換えたTrp2MeSn-基、およびトリプチセン骨格をエテノアントラセン骨格(ジベンゾバレリル基Dbb-)に換えたDbb3Sn-基をそれぞれ合成した。これらの置換基では立体保護効果を保ったまま反応点における立体障害を軽減出来ると期待され、実際スズアニオンの発生がより温和な条件で可能となった他、ジチオエステル等の新しい化合物群の合成が可能となった。

      researchmap

    • 非古典的オニウム種Ph_5Te^+を機軸とする新規超原子価典型元素化合物の合成

      日本学術振興会  科学研究費助成事業 奨励研究(A) 

      箕浦 真生

      詳細を見る

      2000年 - 2001年

      課題番号:12740352

      配分額:600000円 ( 直接経費:600000円 )

      スルホニウムに代表される16族元素オニウム化学種Ph_3Ch^+(Ch=S, Se, Te)は有機化学の発展の過程で古くから研究対象となり用いられてきた。しかしながら超原子価となる16族元素オニウム種Ph_5Ch^+は全く未知であった。本申請課題では中心元素としてテルルを選び、非古典的オニウム種として種々のPh_5Te^+Z^-の合成を行い、性質を明らかにすることを目的とした。
      オニウム種Ph_5Te^+Z^-の合成前駆体としてPh_5TeX(X=F, Cl, Br)の簡便合成法を開発し、テルルーハロゲン結合が共有結合であることを結晶構造解析により明らかにした。このPh_5TeXを用いてPh_5Te^+Z^-(Z=ClO_4, [(CF_3)_2C_6H_3]_4B)の合成をハロゲンの引き抜き反応と続くカウンターアニオン交換により行い、いずれも安定な結晶として単離した。X線結晶構造解析により固体中Ph_5Te^+カチオンのテルル周りではいずれも四角錐構造を有していることが明らかになった。通常の中性5配位典型元素化合物や遷移金属化合物が三方両錐構造を有していることとは対照的であり、これら非古典的オニウム種の特徴と言える。Ph_5Te^+Z^-と求核試剤との反応では対応する中性6価有機テルル化合物を高収率で与え、新しい6価有機テルル化合物の良い前駆体となることがわかった。さらに、容易に得られるようになった中性6価テルル化合物を出発物質として用い、対応する超原子価アニオン種R_5Te^-Y^+およびアニオン種R_4Te^<2->2Y^+(R=4-CF_3C_6H_4,4-CH_3C_6H_4;Y=KC_8)の合成にも初めて成功した。超原子価アニオン種と求電子試剤との反応により、非対称6価有機テルル化合物へ導くなど、反応性を明らかにできた。今後はここで得られた知見に基づき、新規超原子価化合物としの新しい特性の創出へ繋げたいと考えている。

      researchmap

    • 酸化数の異なる5配位有機テルル種の創製とそれらを用いる超原子価化合物の合成と反応

      日本学術振興会  科学研究費助成事業 奨励研究(A) 

      箕浦 真生

      詳細を見る

      1998年 - 1999年

      課題番号:10740296

      配分額:2100000円 ( 直接経費:2100000円 )

      5つの芳香族置換基を有する15族元素(例えばEAr_5,E=P,As,Sb,Bi)や関連するAr_4E^±、Ar_3Te^±などは古くから研究されているものの、対応する超原子価16族元素化合物(Ar_5Te^+またはAr_5Te^-)は全く未知である。最近申請者らが合成した芳香族環を6つ有する元素の初めての例であるTeAr_6の新しい知見に基づき、炭素配位子から成る5配位有機テルル種Ar_5Te^±を合成し、新しい結合様式である超原子価テルルの性質を明らかにする目的で研究を行った。
      本申請課題のAr_5Te^+の合成は昨年度合成に成功した炭素配位子を5つ有するAr_5TeX(Ar=Ph-,p-CF_3C_6H_4-,X=F,Cl,Br)を用いてハロゲンを引き抜くことで合成した。この超原子価カチオン種Ar_5Te^+は驚くべきことに室温下安定に存在し、その構造はX線結晶構造解析により確定し四角錐型構造を有することを明らかにした。溶液中ではBerryの擬回転状態にあること見いだした。また古典的オニウム種Ar_3Te^+との対比から新しい反応性として還元的脱離反応、不均反応などを起こすことが明らかになった。対応するアニオン種Ar_5Te^-はAr_6Teの金属カリウムとの反応により溶液中低温下存在することを各種スペクトルデータおよび反応により確認した。この超原子価アニオン種は炭素官能基化が可能であり新しい6価有機テルル化合物へと導くことが出来た。

      researchmap

    • 炭素配位子からなる6配位有機テルル化合物の合成とリガンドカップリング反応

      日本学術振興会  科学研究費助成事業 奨励研究(A) 

      箕浦 真生

      詳細を見る

      1996年 - 1996年

      課題番号:08740497

      配分額:1000000円 ( 直接経費:1000000円 )

      炭素配位子のみを有する安定な6配位化合物はこれまでに知られていなかった。本研究では超原子価有機16族元素化合物、特にテルルに注目し炭素配位子からなる安定な6配位有機テルル化合物の創製およびその反応性の解明を目的とし、中性で非共有電子対を持たない炭素配位子のみからなる安定な6配位有機テルル化合物の合成を行った。炭素配位子として芳香族置換基、特にパラ位にトリフルオロメチル基を有するp-CF3C6H4-=Arを用い、炭素配位子のみからなる安定な6配位有機テルル化合物としてTeAr6の合成に成功した。TeAr6は対応するArLiにTeCl4を反応させることでone-potで簡便に合成出来、安定な融点320℃の結晶として単離された。TeAr6はX線結晶構造解析により6つのC-Te結合はすべて等価な正八面体構造を有していることが明らかとなり、極めて希なThの対称性を有している。TeAr6は酸素、水および光に対して高い安定性を有しており、融点以下での加熱では全く分解しないものの、350℃の加熱によりラジカル分解生成物に相当する化合物が得られ、また高圧水銀灯による6時間以上の光照射によりTeAr6以外にTeAr2,Ar2等の分解生成物が得られた。これらの挙動はこれまでの2および4配位有機テルル化合物とは全く異なっている。またTeAr6のテルル原子上はハロゲン等にも不活性であり、この6配位状態を保ったまま芳香族環上の官能基化が可能である。今後、3次元的に広がる高い対称性と剛直性、安定性を合わせ持っているTeAr6を核とし、官能基修飾が可能なことを利点とする6配位構造を機軸とする、TeAr6の多修飾機能物質の合成へと展開させる予定である。

      researchmap

    ▼全件表示

    産業財産権

    • チアベンダゾール含有配位高分子

      箕浦 真生, 小林 大哉, 濱川 陽, 柳田 光広

      詳細を見る

      出願人:日本曹達株式会社

      出願番号:特願2020-134883  出願日:2020年8月7日

      公開番号:特開2022-030705  公開日:2022年2月18日

      J-GLOBAL

      researchmap

    • 芳香族酸ポリ無水物及びその製造方法

      猪原 英樹, 箕浦 真生

      詳細を見る

      出願人:東ソー株式会社

      出願番号:特願2019-188795  出願日:2019年10月15日

      公開番号:特開2020-063245  公開日:2020年4月23日

      J-GLOBAL

      researchmap

    • 新規有機テルロニウムおよびセレノニウム化合物

      箕浦 真生, 石井 華, 山本 学, 真崎 康博

      詳細を見る

      出願人:学校法人北里研究所

      出願番号:特願2009-210669  出願日:2009年9月11日

      公開番号:特開2011-057637  公開日:2011年3月24日

      特許番号/登録番号:特許第5515029号  登録日:2014年4月11日 

      J-GLOBAL

      researchmap

    • 新規超原子価テルル化合物

      箕浦 真生, 秋葉 欣哉, 石川 佳代, 小野沢 孝

      詳細を見る

      出願人:東京化成工業株式会社

      出願番号:特願2000-074902  出願日:2000年2月14日

      公開番号:特開2001-226348  公開日:2001年8月21日

      J-GLOBAL

      researchmap

    お問い合わせ先
    外部の方
    学内の方