有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
70 巻 , 9 号
選択された号の論文の11件中1~11を表示しています
巻頭言
総説および総合論文
  • 隅野 幸仁, 福山 高英
    2012 年 70 巻 9 号 p. 896-907
    発行日: 2012/09/01
    公開日: 2012/10/01
    ジャーナル 認証あり
    In the last decade, rapidly evolving microreaction technology based on tiny microchannels has attracted broad attention in organic synthesis. The new technology has also a great potential even for pharmaceutical production because time-saving optimization of flow reaction conditions can be accomplished using an automated microreactor system and the optimal condition can readily be applied to large scale production. A microreaction system also guarantees the quality of products, the operational safety, and the low energy cost. Herein, we report the synthesis of a key intermediate of myriceric acid A, an endothelin receptor antagonist (S-0139) and a matrix metalloproteinase inhibitor (S-3304) using a flow microreactor as model cases. The intermediate of S-0139 was synthesized by Barton reaction using a photo-microreactor and a compact light source, such as a black light or a UV-LED, with high energy efficiency. Using an automated microreactor system, MiChS System X-1, quick optimization of the reaction conditions and the 100 g scale synthesis of the S-3304 by Sonogashira coupling reaction was achieved. We also demonstrate that the flow reaction system using ionic liquid as catalyst support allowed facile separation of products from the catalyst. Large scale synthesis of a key intermediate of S-3304 was also achieved in combination with a micro-extraction/catalyst recycling system, in which the ionic liquid containing the Pd catalyst was continuously recycled. Moreover, parallel synthesis of triazoles by azidation using MiChS System X-1 followed by Huisgen reaction using a batch reactor was successfully carried out.
  • 久木 一朗, 佐々木 俊之, 藤内 謙光, 宮田 幹二
    2012 年 70 巻 9 号 p. 908-917
    発行日: 2012/09/01
    公開日: 2012/10/01
    ジャーナル 認証あり
    Two-fold helical assemblies of points, lines and faces were analyzed by the multipoint approximation method on the basis of three-dimensional space geometry. The analysis has led to the new concept that assemblies generated from a rotational operation by 180 degrees exhibit supramolecular chirality with distinguishable right- or left-handedness, termed as supramolecular tilt chirality, in contrast with the conventional theory in crystallography. This concept has enabled us to determine handedness of two-fold helical assemblies of various organic molecules and macromolecules. Such helical assemblies with three-axial chirality are bundled in various manners through three-stepwise and three-direction processes by using weak interactions. The bundling manners explain formation of chiral crystals starting from achiral molecules, guiding us toward an interpretation of chirality recognition mechanism in host-guest systems. This methodology can unify various kinds of chirality in molecules, supramolecules, macromolecules, and daily life materials on the basis of four-point chirality recognition in three-dimensional space geometry.
  • 仁子 陽輔, 小西 玄一
    2012 年 70 巻 9 号 p. 918-927
    発行日: 2012/09/01
    公開日: 2012/10/01
    ジャーナル 認証あり
    Recently, much attention has been focused on organic fluorescent dyes with a high absorption coefficient and high fluorescent quantum yield, with the aim of using them in fascinating applications, for example, in organic electroluminescence and molecular imaging and as sensors and probes. In 1951, Prof. Zen-ichi Yoshida (Kyoto University) published certain requirements, which are of great significance, for the design of highly fluorescent dyes (Yoshida’s fluorescence rules) in this journal (J. Synth. Org. Chem., Jpn., 9, 230 (1951)). Currently, several modern techniques are available for investigating photophysical processes; therefore, it is necessary to establish sophisticated processes and guidelines for dye design. This review would serve as a guide for the design of highly fluorescent dyes. First, the significance of linear π-extension of aromatic or carbon-carbon multibonds and π-extension of polycyclic aromatic compounds for the synthesis of highly luminescent dyes is emphasized. Second, a Jablonski diagram describing a photophysical process is presented. Two important processes—intersystem crossing and internal conversion—play notable roles in fluorescence enhancement. Third, florescent dyes based on intramolecular charge-transfer complexes are described. Furthermore, a case study on the structure-photoluminescence property relationship for pyrene carbonyl dyes (pyrene with aldehyde, ketone, carboxylic acid, ester, and dialkylamide groups) is presented. The photophysical properties of pyrene modified by carbonyl substituents are successfully revised and systematized by measuring the absolute fluorescence quantum yield in various solvents and by performing density functional theory (DFT) calculations. Moreover, it is demonstrated that the photoluminescence properties of such compounds can be predicted on the basis of TD-DFT calculations.
  • 藤原 哲晶
    2012 年 70 巻 9 号 p. 928-936
    発行日: 2012/09/01
    公開日: 2012/10/01
    ジャーナル 認証あり
    Homogeneous transition-metal catalysts are usually discrete molecules and can be synthesized by ligand design in a defined and rational way. To improve performance of homogenous catalysts, modification of catalysts is usually carried out within a close proximity of a metal center (within a few angstroms). This is effective way to develop efficient catalysts for various reactions including C-C bond-forming reactions and asymmetric reactions. Inspired by these findings, we set out to expand catalytic environment to nanosize by modification of ligands. Here the recent progress in homogeneous transition-metal catalysts with nanosize ligands is overviewed. To expand a molecular size, dendritic frameworks including flexible or rigid moieties, sterically congested m-terphenyl and its higher dendritic framework were introduced onto N-heterocyclic carbene and phosphine ligands.
  • 江口 久雄, 西山 正一, 石川 真一, 曽我 真一, 鯉江 泰行
    2012 年 70 巻 9 号 p. 937-946
    発行日: 2012/09/01
    公開日: 2012/10/01
    ジャーナル 認証あり
    Ttransition-metal catalyzed cross-coupling reactions (C-C, C-N) are the useful and powerful tools for the synthesis of OLED (organic light-emitting diode) or LCD (liquid crystal display) materials. For many years, a major drawback of this reaction has been the poor reactivity of aryl chloride, which are more attractive in terms of cost and availability than the corresponding bromide, iodide and triflate. This review summarized the recent developments combined with our work utilizing the aryl chloride in this area.
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