有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
72 巻 , 12 号
選択された号の論文の12件中1~12を表示しています
巻頭言
総説および総合論文
  • 出水 庸介, 三澤 隆史, 栗原 正明
    2014 年 72 巻 12 号 p. 1336-1347
    発行日: 2014/12/01
    公開日: 2015/01/21
    ジャーナル 認証あり
    Helices in proteins play an important role in a variety of fields such as biology, medicinal chemistry, and organic chemistry. Therefore, stabilized helical peptides have been developed in recent years. As tools for peptide-helix stabilization, non-proteinogenic amino acids such as α,α-disubstituted α-amino acids, cyclic β-amino acids, and cross-linked side chains are often utilized. Herein we report secondary structural control of short peptides using L-amino acids, D-amino acids, α,α-disubstituted α-amino acids, and cross-linked side chains. Furthermore, we applied the stabilized short helical peptides to the catalytic enantioselective epoxidation of α,β-unsaturated ketones, to the inhibitors of vitamin D receptor(VDR)-coactivator interaction, and to the efficient cell-penetrating molecules.
  • 上野 裕, 伊熊 直彦, 小久保 研
    2014 年 72 巻 12 号 p. 1348-1359
    発行日: 2014/12/01
    公開日: 2015/01/21
    ジャーナル 認証あり
    Various types of functionalized fullerenes have been widely developed by considering unique reactivities of the spherical reaction sites; such as not only the enhanced reactivity due to the curved and thus strained C=C double bonds, but also the multiple addition and its electronic control for the selective monoaddition, the regioselectivity controls by spherical π-conjugation and by twisted C=C double bond, the unprecedented substitution mechanism, the highly symmetrical multiple addition via fullerene anion, and the drastic reactivity change by ion encapsulation. The derivatives also proved effective against many potential applications to CMP polishing slurry, antioxidant, anti-inflammatory agent, resist materials, n-type materials for organic photovoltaics, and more.
  • 馬場 章夫, 安田 誠, 西本 能弘
    2014 年 72 巻 12 号 p. 1360-1373
    発行日: 2014/12/01
    公開日: 2015/01/21
    ジャーナル 認証あり
    Four types of synthetic applications of indium(III) salts as characteristic Lewis acids have been discussed. (1) Reductive functionalizations of carbonyl compounds were assisted by a catalytic amount of indium(III) halides, which achieved reductive chlorination and reductive Friedel-Crafts alkylation of aldehydes or ketones, moreover presented reductive allylation and reductive aldol reaction of esters. (2) Direct substitution of hydroxy groups of alcohols and carboxylic acids were also achieved by characteristic interactions between indium trihalide catalyst and silicon moieties. (3) Indium halides catalyzed direct couplings of alcohols with carbon nucleophiles such as enol acetates or 1,3-dicarbonyls were achieved. (4) A novel type of carboindation of alkynes or alkenes was successful, in which direct anti addition of indium tribromide and carbon nucleophiles to alkynes or alkenes takes place.
  • 白川 誠司
    2014 年 72 巻 12 号 p. 1374-1383
    発行日: 2014/12/01
    公開日: 2015/01/21
    ジャーナル 認証あり
    Although quaternary onium salts-catalyzed phase-transfer reactions are generally believed to require base additives, we discovered even without any base additives conjugate additions of 3-substituted oxindoles to nitroolefins proceeded smoothly in the presence of lipophilic quaternary ammonium bromide under water-organic biphasic conditions. The mechanism of this novel base-free neutral phase-transfer reaction system was investigated, and the assumed catalytic cycle was presented together with interesting effects of water and lipophilicity of the phase-transfer catalyst. The base-free neutral phase-transfer reaction system could be applied to highly enantioselective conjugate addition and aldol reactions under the influence of chiral bifunctional ammonium bromides as key catalysts. The efficient approach for the design of chiral quaternary phosphonium bromides as chiral phase-transfer catalysts was also introduced. A catalyst library with various structures has readily been constructed by the use of commercially available chiral phosphines as catalyst precursors. The optimized catalyst has successfully been applied to highly enantioselective conjugate additions and sulfenylation under base-free neutral phase-transfer conditions with low catalyst loading.
  • 朴 昭映, 杉山 弘
    2014 年 72 巻 12 号 p. 1384-1390
    発行日: 2014/12/01
    公開日: 2015/01/21
    ジャーナル 認証あり
    DNA is an attractive chiral source because of its unique helical chirality. Recently, DNA-based hybrid catalysts, self-assembled from DNA and a metal complex with a specific ligand through supramolecular or covalent anchoring strategies, have been developed and applied successfully in a variety of carbon-carbon or carbon-heteroatom bond-forming reactions. Now these enticing biohybid catalysts are expanding their role in asymmetric synthesis. In this review, we summarize the advent and significant progress of DNA-based asymmetric catalysis and discuss remaining challenges for future applications of DNA-based hybrid catalysts.
  • 畠山 琢次, 橋本 士雄磨, 中村 正治
    2014 年 72 巻 12 号 p. 1391-1397
    発行日: 2014/12/01
    公開日: 2015/01/21
    ジャーナル 認証あり
    Polycyclic aromatic compounds possessing heteroatoms are one of the most important materials for organic electronics. Because of the lack of a suitable synthetic methodology, only a few polycyclic aromatic compounds with ring junction heteroatoms, heteroatom-doped nanographenes, have been synthesized to date, even though theoretical investigations have suggested that those molecules are attractive not only as the electronic materials but also as substructures of heteroatom-doped nanocarbons. Herein, we describe development of novel tandem hetero-Friedel-Crafts reactions and their application for the synthesis of heteroatom-fused polycyclic aromatic compounds. These compounds showed strong luminescence or carrier transport ability, thus can be a promissing class of organic materials for optelectronic devices. We have demonstrated their potential utility by fablicating phosphorescent organic light-emitting diodes with a sufficiently high efficiency and a long device lifetime.
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