有機合成化学協会誌

米糠から生産されるフェルラ酸の有用物質への展開

谷口久次, 野村英作, 細田朝夫

2003 年 61 巻 4 号 p. 310-321
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.310

ジャーナルフリー

抄録を表示する抄録を非表示にする

The authors prepared ferulic acid from rice bran pitch which was discharged in a process of the production of edible oil from rice bran and synthesized ethyl 3- (4-geranyloxy-3-methoxyphenyl) -2-propenoate (EGMP) using ferulic acid. EGMP was found to be a chemopreventive agent toward colon cancer in the rats. The condensation products consisting of ferulic and gallic acids showed strong antioxidative effects. Alkyl ferulates showed antimicrobial activity. Amide derivatives of ferulic acid were recognized as compounds accelerating secretion of insulin. The authors also synthesized nine bisferuloyl-myo-inositols, consisting of ferulic acid and myo-inositol moieties, using four key intermediates. These compounds showed the inhibitory effects on generation of tumor promoter 12-O-tetradecanoylphorbor-13-acetate (TPA) -induced superoxide in differentiated HL-60 cells, the suppressive effects on TPA-induced Esptein-Barr virus activation and the suppressive effects on cyclooxgenase-2 promoter activity. The authors prepared the derivative 42 which has i) a polyoxyethylene chain and methoxy groups on the phenyl rings for metal coordination, ii) aromatic rings for a π-π or CH-π interaction, and iii) carboxylic acids as a hydrogen-bonding moiety.

抄録全体を表示

PDF形式でダウンロード (1775K)
イオン応答性フォトクロミック化合物;クラウン化スピロベンゾピラン

田中睦生, 木村恵一

2003 年 61 巻 4 号 p. 322-330
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.322

ジャーナルフリー

抄録を表示する抄録を非表示にする

Various spirobenzopyrans bearing crown ether moieties, namely, crowned spirobenzopyrans, were synthesized and their photochromism was examined in the presence of metal ions. The crowned spirobenzopyrans show facilitated photoisomerization reflecting not only the metal-ion binding ability of the crown ether moiety but also the metal-ion affinity of the phenolate anion moiety in the merocyanine form. When the interaction of metal-ion with the phenolate anion moiety is strong enough, thermal isomerization is observed. Furthermore, this interaction can induce negative photochromism upon UV irradiation. Thus, positive and negative photochromism switching of crowned spirobenzopyrans is possible through the interaction control of metal-ion with the phenolate anion and crown ether moiety.

抄録全体を表示

PDF形式でダウンロード (1321K)
有機マグネシウム反応剤を用いた新規合成反応の開拓

井上淳, 忍久保洋, 大〓幸一郎

2003 年 61 巻 4 号 p. 331-342
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.331

ジャーナルフリー

抄録を表示する抄録を非表示にする

The reaction of β-iodo allylic acetals with EtMgBr in THF afforded tetrahydrofuran derivatives. On the other hand, the reaction in DME provided (3-tetrahydrofuryl) methylmagnesium species that could be trapped by a variety of electrophiles. Treatment of arylmagnesium species with EtMgBr and iodoalkanes in THF afforded 2-aryltetrahydrofurans.ⁿBu₃MgLi induces facile iodine-magnesium exchange at -78°C. ⁱPrⁿBu₂MgLi is more reactive than ⁿBu₃MgLi, and this reagent accomplishes selective bromine-magnesium exchange at -78°C. This procedure was utilized for the preparation of various polyfunctionalized arylmagnesium species. The exchange of alkenyl halides using this method proceeds with retention of configuration at the double bond. The reaction of gem-dibromocyclopropanes with ⁿBu₃MgLi affords butylated cyclopropylmagnesium species that can be trapped with various electrophiles. The reaction of dibromomethylsilanes with ⁿBu₃MgLi in the presence of a catalytic amount of CuCN 2 LiC1 gives α-silylpentylmagnesium compounds that react with electrophiles such as acyl chlorides or α, β-unsaturated ketones to afford α- or γ-silyl ketones respectively. Treatment of dibromodisilylmethanes with Me₃MgLi yields 1-bromo-1, 1-disilylethanes that can be converted into 1, 1-disilylethenes by dehydrobromination.

抄録全体を表示

PDF形式でダウンロード (1781K)
Pincer型ビスオキサゾリニルフェニル (Phebox) を不斉配位子とする光学活性遷移金属ルイス酸錯体の合成と不斉反応への応用

本山幸弘, 西山久雄

2003 年 61 巻 4 号 p. 343-351
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.343

ジャーナルフリー

抄録を表示する抄録を非表示にする

Optically active bis (oxazolinyl) phenyl (Phebox) was designed as an anionic N-C-N pincer ligand, and (Phebox) SnMe₃ was prepared as its stable precursor. The aqua complexes, (Phebox) Rh^IIIX₂H₂O) [X=Cl, Br, F], [(Phebox) M^II (H₂O)] (BF₄) [M=Pd, Pt] and [(Phebox) Pt^IV (H₂O)] (BF₄), were synthesized by the oxidative addition or transmetallation of Rh^I, Pd^II and Pt^II precursors with (Phebox) SnMe₃ and subsequent ligand exchange reaction. X-ray structure studies revealed that the octahedral structure of Rh^III complex is isosteric with the Pt^IV, and the Pd^II and Pt^II complexes are almost the same configuration with a square-planar structure. These aqua complexes acted as efficient catalysts for enantioselective allylation of aldehydes with allyltin reagents, hetero Diels-Alder reaction of Danishefsky's diene with glyoxylates and the aldol-type condensation of tosylmethyl isocyanide with aldehydes. While (Phebox) Rh^III (SnMe₃) Cl complexes catalyzed the Michael addition of α-cyanopropionates to acrolein.

抄録全体を表示

PDF形式でダウンロード (1415K)
特異な構造を有する含窒素芳香族化合物の合成と機能に関する研究

鹿又宣弘

2003 年 61 巻 4 号 p. 352-359
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.352

ジャーナルフリー

抄録を表示する抄録を非表示にする

含窒素芳香族化合物は窒素原子に特異的な反応性・機能性を有するため, 近年効率的な合成法の開発や生体機能関連物質としての応用などに注目が集まっている.筆者らはビニルイミノホスホランの反応を用いることにより, 特異な構造を有する様々な含窒素芳香族化合物の合成法を開発し, 補酵素機能分子の合成, 高立体選択的不斉還元や位置選択的酸化還元を伴う生体モデル系の構築, あるいは架橋型分子の面不斉制御法の開発に焦点を当てて研究を行ってきた.本稿では, 特にシクロファン型の面不斉を有するキラルな架橋型NADHモデル分子の設計・合成と生体不斉還元モデル反応に関する結果と, これに関連する面不斉分子の立体制御法の開発を中、心に, これまで筆者らが行ってきた研究成果の概要を紹介する.
以上のように筆者らは, ビニルイミノホスホランのユニークな複素環形成反応を用いることにより, 様々な含窒素芳香族化合物の合成法を確立した.また, 架橋ニコチンアミドの面不斉に起因する極めて高度な不斉誘導機能を, 補酵素NADHの生体不斉還元モデル系で実現することができた.さらには全く新しい嫌気性解糖型の酸化還元モデル系を構築し, 新しい生体モデル反応の設計概念と手法を導入した.一方, 面不斉制御法の開発により面不斉機能分子の実質的な不斉合成に成功し, この研究の過程でヒドロキシエチルアミドやN-アシルオキサゾリジノンの効率的・選択的な開裂反応を見出した.特に, キラルな架橋ニコチン酸は様々な面不斉分子の合成素子として興味深く, 有機合成化学へのさらなる応用を今後検討してゆく予定である.

抄録全体を表示

PDF形式でダウンロード (1327K)
キノンージアゾアルカン系の反応と合成化学的応用

小久保研, 大島巧

2003 年 61 巻 4 号 p. 360-369
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.360

ジャーナルフリー

抄録を表示する抄録を非表示にする

Quinones are versatile compounds because the conjugated C=O and C=C double bonds are apt to undergo synthetically useful reactions such as 1, 3-dipolar cycloaddition, Diels-Alder reaction, and Michael addition. Diazoalkanes are also useful synthones as a carbene source and a typical dipole in 1, 3-dipolar reactions. Dipolar addition of quinones with diazoalkanes occurs at these double bonds to give oxadiazolines and pyrazolines as the primary adducts. Nitrogen release of these products yields zwitterion intermediates and homoquinones. The zwitterions easily reacted with common alcohols, α, w-diols, and oligoethylene glycols to provide acyclic, cyclic, and crown ether acetals, respectively. On the other hand, homoquinones exhibited photoinduced electron transfer reactions in the presence of some amine and arene donors to afford dimeric products, xanthylium salts, amine adducts, and so on. The enedione structure of homobenzoquinones allowed the [2+2] photocycloadditions with alkenes and alkynes to construct the strained tricyclic diones.

抄録全体を表示

PDF形式でダウンロード (1457K)
十字路

田中睦生, 木村恵一, 本山幸弘, 鹿又宣弘, 小久保研

2003 年 61 巻 4 号 p. 370
発行日: 2003/04/01
公開日: 2009/11/13

DOIhttps://doi.org/10.5059/yukigoseikyokaishi.61.370

ジャーナルフリー

PDF形式でダウンロード (196K)

J-STAGEへの登録はこちら（無料）