Asymmetric Synthesis Using Acetals : Formation of Chiral Oxonium Ion

使用缩醛的不对称合成：手性氧鎓离子的形成

• 批准号: 14572005
• 负责人: FUJIOKA Hiromichi
• 金额: $ 2.24万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14572005/
• 关键词: (R, R)-hydrobenzoin; asymmetric desymmetrization; stenine; scyphostatin; acyclic σ-symmetic diene acetal; domino haloetherification; optically active tetrahydrofuran; シクロヘキサジエンアセタール; 3-エンドフェニルノルボルネンアルデヒド; メソ-ジオール

Formations of chiral oxonium ion intermediates by intramolecular haloetherification of ene acetals and their applications have been investigated.As an application of the chiral, non-racemic cyclohexene acetal obtained by an intramolecular haloetherification reaction of cyclohexadiene acetal from 3-(1,4-cyclohaxadien-3-yl)propanal and chiral hydrohenzoin, synthetic work of stemona alkaloids was held. As a result, 9a-epi-stenine has been achieved, and the synthesis of stenine itself is on the last stage. From the intermediate of their syntheses, the epoxy cyclohexenone core of scyphostatin having N-Smase inhibiting activity was synthesized.Furthermore, an unexpected domino intramolecular haloetherification reaction of acyclic σ-symmetic diene acetals was found, and the tetrahyderofurans having four asymmetric centers were obtained in one-pot operation.

研究了烯缩醛分子内卤代醚化反应生成手性氧鎓离子中间体及其应用，并以3-（1，4-环己二烯-3-基）丙醛与手性氢化苯偶氮化合物环己二烯缩醛分子内卤代醚化反应生成手性非外消旋环己烯缩醛为例，开展了百部生物碱的合成工作。结果，9 α-表-斯泰宁已经实现，斯泰宁本身的合成已进入最后阶段。以它们的中间体为原料，合成了具有N-Smase抑制活性的scyphostatin的环氧基环己烯酮核，并发现了无环σ-对称二烯缩醛的多米诺分子内卤代醚化反应，一锅法合成了具有4个不对称中心的四氢呋喃。

项目成果

Unexpected Reaction of 2,3-Eposysulfonates : Novel Formation of Two Enones with Reversed Substituents an α- and β-Position from the Single Isomer

2,3-环氧磺酸盐的意外反应：从单一异构体新形成具有反向取代基（α-和β-位）的两个烯酮

• 发表时间: 2004
• 期刊: Heterocycles 62
• 作者: H.Fujioka;Y.Ohba;J.Futamura;Yasuyuki KIta
• 通讯作者: Yasuyuki KIta

Acid-catalyzed Rearrangement of Epoxy Alcohol Derivatives Having the Electron-withdrawing Protective Group (Acyk of Sulfonyl): Asymmetric Synthesis of Chiral Quaternary Carbon and Spiro Centers and Its Application to Natural Products Synthesis

具有吸电子保护基团（磺酰基酰基）的环氧醇衍生物的酸催化重排：手性季碳和螺中心的不对称合成及其在天然产物合成中的应用

• 发表时间: 2003
• 期刊: J.Syn.Org.Chem.(Japan) 61
• 作者: H.Fujioka;Y.Yoshida;Y.Kita
• 通讯作者: Y.Kita

FUJIOKA, Hiromichi: "Unexpected Reaction of 2,3-Epoxysulfonates : Novel Formation of Two Enones with Reversed Substituents at α- and β-Position from the Single Isomer"Heterocycle. 62. 453-462 (2004)

FUJIOKA, Hiromichi：“2,3-环氧磺酸盐的意外反应：从单一异构体的 α-和 β-位上具有反向取代基的两个烯酮的新形成”杂环。 62. 453-462 (2004)

Concise asymmetric synthesis of a model compound, (4S,5S,6S)-6-(2,2-dimethoxy)ethyl-4,5-epoxy-6-hydroxy-2-cyclohexenone, for the cyclohexenone core of scyphostatin

• DOI: 10.1016/s0040-4039(02)00916-4
• 发表时间: 2002-07-01
• 期刊: TETRAHEDRON LETTERS
• 影响因子: 1.8
• 作者: Fujioka, H;Kotoku, N;Kita, Y
• 通讯作者: Kita, Y

FUJIOKA, Hiromichi: "Kinetically Controlled Optical Resolution of Racemic Norbornene Aldehyde Derivatives"Chirality. 15. 60-67 (2003)

FUJIOKA, Hiromichi：“外消旋降冰片烯醛衍生物的动力学控制光学拆分”手性。