Study on generation of conjugated heterocumulene

共轭杂积烯的生成研究

• 批准号: 12470484
• 负责人: SATO Masayuki
• 金额: $ 1.54万
• 依托单位: University of Shizuoka
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12470484/
• 关键词: heterocumulene; acyl ketene; cycloaddition; 1,3-dioxin-4-one; pyridinophane; crown ether; macrocycle; シクロファン; 熱分解; アンサ型化合物; ケテン; 不斉認識; 光学分割; 面性不斉

1) A series of prochiral 2, 2-bis(hydroxylmethyl)-1, 3-dioxin-4-ones was synthesized by [4+2]cycloaddition of acylketene to protected 1, 3-dihydroxy-2-propanones followed by deprotection of the hydroxyl groups. Dissymmetrization of the prochiral dioxinones by lipase-catalyzed monoacetylation afforded optically active 2-(hydroxymethyl)dioxinones. Intramolecular photo[2+2]cycloaddition of the alkenoates of these alcohols provided an efficient method for regio-, diastereo-, and enantioselective synthesis of cyclobutanols.2) 4-Hydroxy-2-pyrone derivative bridged by polymethylenes at the 3- and 6-positions are readily synthesized by intramolecular [4+2]cycloaddition of bis(acylketene). On heating with ammonia, the bridge 2-pyrones afforded the corresponding 2, 6-bridged 4-pyridones. This methods have a wide applicability to the bridge length; compounds with a short bridge (n = 8) as well as long bridge (n = 18) are synthesized in satisfactory yields.3) Dehydroacetic acid derivative bridged by di(ethylene glycol) unit was synthesized by intramolecular [4+2]cycloaddition of a bis(acylketene). Heating the bridged dehydroacetic derivative with ammonia afforded crown ether type pyridinophane (12-crown-4).

1) 通过将酰基乙烯酮与受保护的1, 3-二羟基-2-丙酮进行[4+2]环加成，然后脱保护，合成了一系列前手性2, 2-双(羟甲基)-1, 3-二恶英-4-酮。羟基。通过脂肪酶催化的单乙酰化作用使前手性二恶酮不对称化，得到光学活性的 2-(羟甲基)二恶酮。这些醇的烯酸酯的分子内光[2+2]环加成反应为环丁醇的区域选择性、非对映选择性和对映选择性合成提供了一种有效的方法。2) 4-羟基-2-吡喃酮衍生物在3-和6位由多亚甲基桥联-位很容易通过双(酰基乙烯酮)的分子内[4+2]环加成合成。用氨加热时，桥接2-吡喃酮得到相应的2, 6-桥接4-吡啶酮。该方法对桥梁长度有广泛的适用性；合成了短桥（n = 8）和长桥（n = 18）的化合物，收率令人满意。3）通过分子内[4+2]环加成合成了二（乙二醇）单元桥联的脱氢乙酸衍生物双(酰基乙烯酮)。将桥联脱氢乙酸衍生物与氨一起加热，得到冠醚型吡啶并芬(12-冠-4)。

项目成果

M.Sato, T.Oda, K.Iwamoto, S.Fujii: "A new method for synthesis of crown ether type pyridinophanes"Heterocycles. 60(in press). (2003)

M.Sato，T.Oda，K.Iwamoto，S.Fujii：“一种合成冠醚型吡啶并芬的新方法”杂环。

M.Sato, T.Oda, K.Iwamoto, E.Murakami: "Highly efficient methods for metacyclophane synthesis"Tetrahedron. 59(in press). (2003)

M.Sato、T.Oda、K.Iwamoto、E.Murakami：“高效合成间环芳烷的方法”四面体。

M.Murakami, H.Kamaya, C.Kaneko, M.Sato: "Synthesis of optically active 1,3-dioxin-4-one derivatives having Hydroxymethyl group at the 2-position and their use for regio, stereo, and enantio-selective synthesis of cyclobutanols"Tetrahedron : Asymmetry. 14.

M.Murakami、H.Kamaya、C.Kaneko、M.Sato：“2 位具有羟甲基的光学活性 1,3-二恶英-4-酮衍生物的合成及其在区域、立体和对映异构体中的应用

M.Sato., K.Iwamoto.: "Development in ketene chemistry"J. Synth. Org. Chem. Japan. 57. 76-83 (1999)

M.Sato.，K.Iwamoto.：“乙烯酮化学的发展”J.

M.Sato., T.Oda., K.Iwamoto., E.Murakami.: "Highly Efficient Methods for Metacyclophane Synthesis"Tetrahedron, (in press). 59. (2003)

M.Sato.、T.Oda.、K.Iwamoto.、E.Murakami.：“高效合成间环芳烷的方法”Tetrahedron，（正在印刷中）。