有機合成化学協会誌
Online ISSN : 1883-6526
Print ISSN : 0037-9980
ISSN-L : 0037-9980
検索
詳細検索
OR
閲覧
検索
68 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
すべての抄録を表示する
    • |<
    • <
    • 1
    • >
    • >|
巻頭言
総説および総合論文
  • イソニトリル金属錯体と有機合成化学への応用
    伊藤 嘉彦
    2010 年 68 巻 12 号 p. 1239-1248
    発行日: 2010/12/01
    公開日: 2011/02/01
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.68.1239
    ジャーナル 認証あり
    抄録を表示する抄録を非表示にする
    This account outlines our studies on isonitrile-metal complexes and their application to organic synthesis.
    Isonitriles possess an electronic structure which is similar to that of carbon monoxide. The carbene character brings about versatile reactivities as the reagent and interesting properties as the ligand. The α-hydorogen is highly acidic, and hence, the α-position is endowed with a nucleophilic character. Reduction of an alkylisonitrile with tin hydride affords alkane via a radical mechanism. Various organometallic reagents undergo α-addition to isonitriles and the resulting imidoylmetal intermediate acts as the acyl anion equivalent. Insertion of isonitriles into an Si-Si bond is catalyzed by palladium. A highly enantioselective aldol reaction of α-isocyanoesters with aldehydes is achieved by a gold catalyst. Isonitrile-Pd(0) complexes efficiently activate Si-Si and Si-B linkages, and unsaturated functionalities are inserted therein. Aromatizing polymerization of 1,2-diisocyanoarenes produces poly(quinoxaline)s which possess chiral helical structures. Enantiomerically enriched ones are successfully synthesized by using a chiral catalyst or auxiliary.
    抄録全体を表示
    PDF形式でダウンロード (1188K)
  • 生物活性天然有機化合物の機能解明を指向した実践的合成手法の開発
    難波 康祐
    2010 年 68 巻 12 号 p. 1249-1260
    発行日: 2010/12/01
    公開日: 2011/02/01
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.68.1249
    ジャーナル 認証あり
    抄録を表示する抄録を非表示にする
    The limited supplies of biologically active natural products from natural source have been a severe bottleneck for their application to medical care or mechanistic study of their functions. Synthetic organic chemistry may become a best possible solution of this supply problem by the development of practical synthetic methods suited to the intended molecules. For right-half of halichondrin B, we established a new catalytic cycle of Cr-mediated coupling reaction, new asymmetric Ni/Cr-mediated coupling reaction, surprisingly efficient catalytic Cr-mediated coupling reaction, catalytic Ni/Cr-mediated macrocyclization without use of high-dilution techniques, and effective device for forming polycyclic ring system of halichondrin B. For mugineic acid, we established the practical synthesis of 2'-deoxy mugineic acid with minimal requirements for workup and purification procedure, efficient synthesis of mugineic acid, and synthesis of mugineic acid derivatives as molecular probes. For E-ring of palau'amine, we established Hg(OTf)2-catalyzed olefin cyclization reactions, and its application to the construction of tetra-substituted carbon center possessing nitrogen that corresponds to C16 position of palau'amine.
    抄録全体を表示
    PDF形式でダウンロード (1488K)
  • 新規メカニズムに基づく難治性そう痒症治療薬ナルフラフィン塩酸塩の創出
    長瀬 博, 川村 邦昭, 河合 孝治, 早川 潤
    2010 年 68 巻 12 号 p. 1261-1271
    発行日: 2010/12/01
    公開日: 2011/02/01
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.68.1261
    ジャーナル 認証あり
    抄録を表示する抄録を非表示にする
    Nalfurafine hydrochloride (1) was launched on March of 2009 in Japan as the first in class non-narcotic opioid drug for intractable itch caused by haemodialysis. Rational medicinal chemistry effort led us to obtain the morphinan derivative, which is a new chemical class of opioid κ-agonist without the [N-C-C-N(sp2)] pharmacophore sequence of the typical U-50488H derivatives. The applicability of “Message-Address Concept” and “Accessory Site Hypothesis” in the development of the opioid κ-agonist could also be proven. Nalfurafine hydrochloride (1) showed significant opioid κ-agonist activity and induced neither aversion nor preference in rats on the CPP (Conditioned Place Preference) test. No dependence sign was observed in monkey on the self-administration test. This compound was approved without legal narcotic nor psychotropic drug control after a clinical evaluation on human. Details on design rationale and medicinal chemistry of this novel drug will be discussed.
    抄録全体を表示
    PDF形式でダウンロード (1456K)
  • 機能性ニトロンを用いたアミノ酸型天然物の合成研究
    田村 修
    2010 年 68 巻 12 号 p. 1272-1285
    発行日: 2010/12/01
    公開日: 2011/02/01
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.68.1272
    ジャーナル 認証あり
    抄録を表示する抄録を非表示にする
    (5R)- [and (5S)]-5,6-Dihydro-5-phenyl-2H-1,4-oxazin-2-one N-oxides were designed and synthesized as chiral (E)-geometry-fixed α-alkoxycarbonylnitrones that exist as equilibrating mixture of (E)- and (Z)-isomers. The cyclic nitrone reacted with olefins under mild conditions to afford the main cycloadducts via the least sterically demanding exo modes. The nitrone also reacted with an allyl alcohol in the presence of magnesium bromide from the less hindered face via exo-mode to afford exclusively cycloadduct as a single stereoisomer. These reactions were applied to the syntheses of carbocyclic polyoxin C, anti-β-substituted aspartic acid, clavalanine, monatin, lycoperdic acid, neodysiherbaine A, and maremycins A and D1.
    抄録全体を表示
    PDF形式でダウンロード (1507K)
  • 後周期遷移金属触媒を用いた置換アセチレン重合の新展開
    塩月 雅士, 尾西 尚弥, 三田 文雄
    2010 年 68 巻 12 号 p. 1286-1294
    発行日: 2010/12/01
    公開日: 2011/02/01
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.68.1286
    ジャーナル 認証あり
    抄録を表示する抄録を非表示にする
    This article overviews the new aspects of transition metal catalysts for polymerization of substituted acetylene monomers. The activity of rhodium-based catalysts is enhanced by introducing a strongly π-acidic diene ligand, tetrafluorobenzobarrelene (tfb). Precise control of polymerization of phenylacetylenes is achieved by two types of rhodium catalysts bearing tfb. The activity of zwitterionic rhodium-type catalyst is also intensified by the introduction of tfb, which achieves a higher monomer consumption rate than that with the conventional rhodium catalyst. Disubstituted acetylenes with polar functional groups are polymerized by well-defined ruthenium carbene catalyst. Phenylacetylenes having a coordinative substituent at the ortho position on its aromatic ring are efficiently polymerized by the ruthenium carbene catalyst to give the corresponding polymers in high yields.
    抄録全体を表示
    PDF形式でダウンロード (1055K)
  • アンモニウム基を介した環状アリルアミン，ホモアリルアミンの酸化
    黒澤 渉, Paul M. Roberts, Stephen G. Davies
    2010 年 68 巻 12 号 p. 1295-1306
    発行日: 2010/12/01
    公開日: 2011/02/01
    DOIhttps://doi.org/10.5059/yukigoseikyokaishi.68.1295
    ジャーナル 認証あり
    抄録を表示する抄録を非表示にする
    We have developed a metal-free and highly diastereoselective ammonium-directed dihydroxylation of 3-aminocyclohex-1-enes upon treatment with Cl3CCO2H followed by mCPBA. The reaction mechanism involves protection of the amine by protonation, hydrogen-bonded delivery of the oxidant by the allylic ammonium ion formed in situ, followed by highly regioselective ring-opening of the intermediate syn-epoxide by trichloroacetic acid, to give a 1,2-anti-2,3-syn amino diol after deprotection. Meanwhile, oxidation of the corresponding tertiary amine N-oxide is entirely complementary and proceeds with high anti-diastereoselectivity to afford the corresponding 1,2-anti-2,3-anti amino diol after deprotection, consistent with the epoxidation reaction proceeding under steric or dipole control. The ammonium-directed oxidation protocol is general for a range of cyclic allylic and homoallylic amines and facilitates the metal-free synthesis of all four diastereoisomers of the corresponding 3-amino-1,2-diols, and has recently been employed as one of the key steps in the syntheses of (±)-1-deoxynojirimycin and (±)-1-deoxyaltronojirimycin.
    抄録全体を表示
    PDF形式でダウンロード (1189K)
Review de Debut
ラウンジ
十字路
反応機構演習
    • |<
    • <
    • 1
    • >
    • >|
feedback
 Top