有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
68 巻, 8 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
  • 大山 俊幸
    2010 年 68 巻 8 号 p. 802-813
    発行日: 2010/08/01
    公開日: 2010/10/12
    ジャーナル 認証あり
    Photosensitive polyimides have been used to form thermally and mechanically stable fine patterns utilized for such as buffer-coat layers and inter-layer dielectrics in electronic devices. Conventional photosensitive polyimides usually contain poly(amic acid)s as polyimide precursors or functionalized polyimides as their polymer component. Here, we report a novel design for preparation of photosensitive polyimides, reaction development patterning(RDP). RDP utilizes nucleophilic acyl substitution reaction of nucleophiles in developer with imide groups in polyimides as the key reaction of pattern formation, and therefore, no introduction of specific functional groups into polyimide framework is needed. In addition, RDP can afford photosensitivity to engineering plastics having carboxylic-acid-derivative linkages other than polyimide. We have developed both positive- and negative-tone RDPs. Positive-tone RDP utilizes main-chain scission of engineering plastics by amines in developer for pattern formation. Negative-tone RDP realizes higher sensitivity with smaller amount of photosensitive agent than positive-tone RDP. Application of industrially-used alkaline developer to negative-tone RDP is also achieved. Further reduction of the amount of photosensitive agent with increasing sensitivity is examined by introduction of chemical amplification mechanism to RDP.
  • 早川 一郎, 木越 英夫
    2010 年 68 巻 8 号 p. 814-823
    発行日: 2010/08/01
    公開日: 2010/10/12
    ジャーナル 認証あり
    Haterumalides, isolated from Okinawan marine animals, are 14-membered macrolides with strong cytotoxicity against human cancer cell lines. We have achieved the total synthesis of haterumalides NA and B by using B-alkyl Suzuki-Miyaura coupling and Nozaki-Hiyama-Kishi coupling as key steps. Compared to our first-generation approach for ent-haterumalide NA methyl ester, this second-generation synthesis yielded the key intermediate in much better yield. This synthesis also established the relative stereochemistry of haterumalide B. Furthermore, the structure-cytotoxicity relationships of haterumalides were investigated. The combination of macrolide and side chain parts proved to be important to the strong cytotoxicity.
  • 西口 郁三
    2010 年 68 巻 8 号 p. 824-833
    発行日: 2010/08/01
    公開日: 2010/10/12
    ジャーナル 認証あり
    This review consists of a number of highly selective and useful new organic synthetic reactions, which are characteristic with particular and selective reactivities and behaviors of radical ions intermediates, generated by transfer of one electron between organic molecule and electrodes, magnesium metal. Those reactions are also quite difficult or almost impossible to realize through usual carbocation, carbanion or radical intermediates, and may be classified as one of new fields, namely “Organic Synthesis by Organic Electron Transfer Chemistry”.
  • 新谷  亮
    2010 年 68 巻 8 号 p. 834-844
    発行日: 2010/08/01
    公開日: 2010/10/12
    ジャーナル 認証あり
    Intermolecular cycloadditions catalyzed by transition-metal complexes are powerful methods for convergent synthesis of cyclic materials. In this context, we recently devised γ-methylidene-δ-valerolactones as new reagents for intermolecular decarboxylative cyclization reactions with several reaction partners to produce various cyclic compounds under palladium catalysis. These lactones effectively serve as precursors for 1,4-zwitterionic species through oxidative addition to palladium(0) and successive decarboxylation, thereby introducing a four-carbon unit in a newly formed cyclic framework. In some cases, however, they provide three carbons in a cyclic framework with a spirocyclopropane moiety. Herein we describe an overview of the reactions using these lactones, including some asymmetric variants as well as mechanistic insights for these decarboxylative cyclization reactions.
  • 村田 美樹, 増田 弦
    2010 年 68 巻 8 号 p. 845-853
    発行日: 2010/08/01
    公開日: 2010/10/12
    ジャーナル 認証あり
    Since arylsilanes are versatile reagents for carbon-carbon bond formation, the supply of functionalized and reactive arylsilanes has become more necessary. We demonstrated the first example of the palladium(0)-catalyzed silylation of aryl halides with triethoxysilane as a silicon source and affording the corresponding aryltriethoxysilanes. Although this catalyst system has lacked the wide applicability to functionalized substrates, we found that a rhodium(I) complex overcomes a number of limitations of the palladium(0)-catalyzed silylation. The silylation of aryl iodides with hydrosilanes was able to apply to 1,1,1,3,5,5,5-heptamethyltrisiloxane by the appropriate choice of catalyst systems. 3-Aryl-1,1,1,3,5,5,5-heptamethyltrisiloxanes were also provided by platinum-catalyzed dehydrogenative coupling with aromatic hydrocarbons. These catalytic silylations supply a wide range of functionalized arylsiloxanes.
  • 小関 稔, 野出 學
    2010 年 68 巻 8 号 p. 854-865
    発行日: 2010/08/01
    公開日: 2010/10/12
    ジャーナル 認証あり
    In this article, we describe asymmetric syntheses taking advantage of chiral auxiliary characteristics. In the asymmetric Michael addition reaction of chiral thiol, we developed a novel tandem Michael-MPV (Meerwein-Ponndorf-Verley) reaction, which provided the 1,3-mercaptoalcohols with two or three chiral centers. Moreover, multi-contiguous chiral centers were finely constructed in one pot utilizing three types of Michael addition-initiated reactions, i.e., tandem Michael-aldol reaction, double Michael addition reaction, double Michael-aldol reaction, which were triggered by a nucleophilic attack of a novel recyclable chiral amine. Asymmetric syntheses of a number of biologically active compounds such as captopril, γ-lactone natural products, (+)-negamycin and β-lactam were achieved as an application of our reactions.
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