有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
67 巻, 10 号
選択された号の論文の10件中1~10を表示しています
巻頭言
総説および総合論文
  • 勝山 勇
    2009 年 67 巻 10 号 p. 992-1000
    発行日: 2009年
    公開日: 2010/07/12
    ジャーナル 認証あり
    Heteroaromatic compounds are widely distributed in nature and often found in numerous biologically active natural products, agrochemicals, drugs, dyes, polymers, etc. because they usually have various chemical and physicochemical properties. In particular, pyridines are one of the most important heteroaromatic compounds and thus widely applied as biologically active compounds and organic materials. Trifluoromethyl-containing heteroaromatic compounds often have extremely unique properties and therefore have been studied during the last several decades. In fact, some of such compounds are currently widely utilized as commercialized agrochemicals, drugs etc. as well as drug candidates under development. This review introduces synthesis of several trifluoromethyl-containing pyridines and their applications to biologically active molecules.
  • 南方 聖司
    2009 年 67 巻 10 号 p. 1001-1011
    発行日: 2009年
    公開日: 2010/07/12
    ジャーナル 認証あり
    Heteroatom–halogen bonds were successfully utilized for efficient and convenient synthesis of heterocycles and aminohalogenated compounds from readily available reagents. The direct aziridination of olefins with N–chloro–N–sodio–p–toluenesulfonamide (chloramines–T: CT) in the presence of iodine catalyst has been achieved, and the method was applied to a green process using silica–water as the reaction media. N–Chloro–N–sodiocarbamates reacted with electron–deficient olefins in the presence of a phase transfer catalyst to give the corresponding aziridines, and the method was applied to the asymmetric synthesis. Fullerene, C60, was also aziridinated by using active reagents containing N–X bonds, and the resulting aziridinofullerenes underwent a unique rearrangement to azafulleroids. Moreover, unique aminohalogenation of olefins utilizing chloramines–T and bromamine–T under an atmosphere of carbon dioxide was also revealed. Treatment of alkenylamides with tert–butyl hypoiodite led to the production of various N–heterocycles. Iodination of readily available sulfonamides or carboxamides with tert–butyl hypoiodite generated reactive N–iodinated amides, which reacted with olefins to give aziridines or oxazolines.
  • 川崎 知己
    2009 年 67 巻 10 号 p. 1012-1024
    発行日: 2009年
    公開日: 2010/07/12
    ジャーナル 認証あり
    The pyrrolino [2,3–b] indoline ring system bearing an allylic moiety at the 3a–site is a widely distributed structural framework present in a number of biologically active natural products. In view of the potential of these compounds as a lead compound to new and more biologically active agents, a development of diversely and efficiently synthetic methods for pyrrolino [2,3–b] indolines and analogues is essential. This review describes an efficient methodology for construction of pyrrolino [2,3–b] indoline architecture through a domino reactions, Horner–Wadsworth–Emmons olefination of 2–allyloxy–3–indolinone, isomerizetion, Claisen rearrangement and a reductive cyclization of oxindoles having C2N and allylic units at 3–site. This methodology was applied to total syntheses of the related natural products, pseudophrynaminol and flustramine A–C. Furthermore, total syntheses of pyrazino [2′,1′–5,1] pyrrolino [2,3–b] indoline natural products, fructigenine A and 5–N–acetylardeemin through Ugi reaction and cyclization are also illustrated.
  • 伊津野 真一
    2009 年 67 巻 10 号 p. 1025-1032
    発行日: 2009年
    公開日: 2010/07/12
    ジャーナル 認証あり
    The heterogeneous chiral catalysts for the synthesis of optically active compounds have been energetically developed mainly due to their easy separation and recycle use. However, the supported catalysts sometimes lead to negative effects both on the reactivity and the enantioselectivity. Design of the polymer–support is important issue to develop essentially useful polymeric chiral catalyst. We have designed novel polymer–immobilized chiral catalysts based on the use of amphiphilic polymer support. For example, polymers having quaternary ammonium sulfonate pendant groups were efficiently used as suitable polymer support of the chiral catalyst for the reactions in aqueous solution. By using of the amphiphilic polymer–immobilized chiral catalyst, asymmetric transfer hydrogenation in water smoothly occurred to give the corresponding optically active alcohol with positive effect on the enantioselectivity. When the enantiopure quaternary ammonium sulfonate was introduced into polymer, asymmetric alkylation of glycine derivatives can be catalyzed by the chiral ammonium polymer. Chiral quaternary ammonium cation was attached to polymeric sulfonate anion through ionic bonding. This immobilization method using ionic bond is substantially useful since any type of chiral quaternary ammonium structure can be immobilized into polymer without any additional chemical modification on the catalyst molecule.
  • 平尾 明, 渡部 拓海, Hee–Soo Yoo
    2009 年 67 巻 10 号 p. 1033-1043
    発行日: 2009年
    公開日: 2010/07/12
    ジャーナル 認証あり
    Dendrimer–like hyperbranched polymers (DBP)s have recently appeared as a new class of hyperbranched polymers. Although (DBP)s resemble dendrimers in branched architecture, they are composed of polymer chains between junctions and, accordingly, much higher in molecular weight and much larger in molecular size than dendrimers. Because of their specific hyperbranched structures and nano–size globular molecular shapes, (DBP)s have attracted much attention due to specialty functional materials and supra–structured nano–materials with many potential applications. In this review article, precise syntheses of DBP by previously reported procedures and recently developed new methodology based on “arm–first” divergent approach are highlighted. Furthermore, the possible synthesis of various (DBP)s having different branched architectures and polymer chains are introduced. Finally, their solution properties, sizes, and shapes are discussed.
  • 金原 数
    2009 年 67 巻 10 号 p. 1044-1052
    発行日: 2009年
    公開日: 2010/07/12
    ジャーナル 認証あり
    Ferrocene, a double–decker organometallic compound that generates an angular motion, can be used as a unique rotary module for molecular machines. Actually, we have developed novel molecular machines that consist of photochromic and 1,1′, 3,3′–tetrasubstituted ferrocene units. Since 1,1′, 3,3′–tetrasubstituted ferrocene derivatives are chiral, their conformational changes are able to be monitored by circular dichroism spectroscopy. As photochromic units, we adopted azobenzene and diarylethene derivatives, which undergo elongation/contraction motions in response to UV/visible light. Thus, the motions of the photochromic units accompanied by the photoisomerization processes can be transferred to the ferrocene unit to generate an angular motion, by taking advantage of interlocking a ferrocene–based rotary module with a photochromic unit through both covalent and non–covalent bond. This design strategy, which mimics real artificial machines in our daily life, would allow for not only design of gigantic molecular machines and but also remote control of molecular events.
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