有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
48 巻 , 3 号
選択された号の論文の7件中1~7を表示しています
  • 村上 章, 牧野 圭祐
    1990 年 48 巻 3 号 p. 180-193
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
    In this short review, recent developments in the syntheses of antisense DNAs are described. The antisense DNA/RNA method is one of the ways to regulate gene expression specifically and uses sequence specific DNAs and their analogs, namely antisense DNAs. They have been designed and synthesized in order to meet requirements, for use in living systems, such as selectivity, nuclease resistance, cell membrane permeability, and duplex stability. The design is mainly focused on the modification of phosphate backbones, the modification of sugar moieties, and the introduction of functional molecules into antisense DNAs. The ability of these antisense DNAs to regulate gene expression are also discussed as well as biological studies.
  • 大和 隆志, 杉山 亨, 須賀 亮, 大塚 雅巳, 大野 雅二
    1990 年 48 巻 3 号 p. 194-205
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
    Bleomycins (BLMs) are antitumor antibiotics of unusual glycopeptide structure. The potent activity of BLM is attributed to the oxygen activation and the DNA cleavage by the formation of iron-chelate of the peptide moiety. erythro-β-Hydroxy-L-histidine, a pivotal amino acid for the oxygen activation, is prepared enantioselectively by aldol reaction of (R) -3-bromoacetyl-4-isopropyl-1, 3-oxazolidin-2-one with 1-triphenylmethylimidazole-4-carbaldehyde. Model ligands for the metal binding site of BLM with 4-methoxypyridine (PYML-6) and 4-dimethylaminopyridine (PYML-8) show oxygen activation up to 97% and 125% of that of BLM, respectively. cis-β-Methylstyrene is oxidized either with Fe (III) -H2O2 or Fe (II) -O2 complex systems of BLM and PYML-6 to give the corresponding optically active epoxide. The DNA binding region of BLM is combined with PYML-6 to give the first man-designed BLM, PYML (6) -bleomycin, which shows nucleotide cleavage mode remarkably similar to that of BLM. On the other hand, PYML-6 moiety and distamycin are coupled to afford PYML (6) - (4R-APA) -distamycin which shows dramatically altered AT specific mode in the DNA scission.
  • 二宮 一彌, 内藤 猛章, 木口 敏子, 宮田 興子
    1990 年 48 巻 3 号 p. 206-215
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
    A general total synthetic methodology for indole alkaloids via the route involving reductive photocyclization of enamides has been developed. Acylation of imines such as harmalane and tricyclic imine with either p-methoxybenzoyl or 3-furoyl chloride followed by reductive photocyclization furnished the compounds having skeletal structures of indole alkaloids, yohimbines and ergolines. They were then readily converted, upon modification of either methoxylated dihydrobenzene or dihydrofuran ring to respective alkaloids including yohimbine, alloyohimbine, deserpidine, and 19, 20-dehydroyohimbine in one group and lysergic acids, elymoclavine, agroclavine, lysergols, lysergines, and fumigaclavines in another group.
  • 浅岡 守夫, 武井 尚
    1990 年 48 巻 3 号 p. 216-228
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
    予期したように1のトリメチルシリル基はシクロヘキサノン環の構造を固定することにより種々の置換基の立体選択的導入を可能とし, 更に環開裂の際には位置選択性に貢献する。また, 時には合成中間体の結晶性をあげ再結晶による光学純度の向上も可能としている。また, 天然物合成の項で一部示したようなものを始めとして, 様々な形の変換が可能であり, 更に広範囲の光学活性体合成への応用が可能と考えられる。しかしながら構造によってはトリメチルシリル基の除去に労力を要する場合もあり, それらの点を改善し, 更に応用範囲を広げることを目的として現在, 他の置換基を持つシリル基の導入や他の環員数の類縁体の合成とそれらの反応性についても検討を行っているが, これらの結果については機会を改めて報告したい。以上, 本報文が種々の光学活性天然物, 生理活性化合物合成の際に多少なりとも参考となれば幸いである。
  • 上方 宣政, 清水 敏夫
    1990 年 48 巻 3 号 p. 229-239
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
    Some optically active diaryl selenoxides stabilized by bulky oitho substituents such as isopropyl or t-butyl group were obtained by fractionary recrystallization or by chromatographic resolutions. Optically active alkyl aryl selenoxides were synthesized by asymmetric oxidation of corresponding selenides under Sharpless oxidation conditions The absolute configurations of these optically active selenoxides were determined by X-ray diffraction and circular dichroism spectra. The rate of racemization of the optically active selenoxide under several conditions were investigated, and the mechanism involving achiral hydrate was clarified by H218O studies.
  • 酒井 健一, 村上 尚道
    1990 年 48 巻 3 号 p. 240-242
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
  • 村上 章, 大塚 雅巳, 大野 雅二, 浅岡 守夫
    1990 年 48 巻 3 号 p. 243
    発行日: 1990/03/01
    公開日: 2009/11/13
    ジャーナル フリー
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