Development of highly effective rhodium-catalyzed reaction and its application

高效铑催化反应的研制及其应用

• 批准号: 13672243
• 负责人: IKEDA Masazumi
• 金额: $ 2.24万
• 依托单位: Kyoto Pharmaceutical University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672243/
• 关键词: dirhodium(II) catalyst; C-H insertion reaction; chemo- and stereo-selective; α-diazoketone; cyclpentanone; 3(2H)-furanone; β-hydroxy acid; cyclization; αーアルコシキジアゾケトン; ロジウム(II)触媒C-H挿入反応; 2-ジヒドロフラノン; 不斉合成; 無溶媒Baeyer-Villiger反応; 抗腫瘍活性海洋天然物; dic

Development of novel highly chemo- and stereo-selective dirhodium(II)-catalyzed C-H insertion reaction of α-diazoketones controlled by stereo-electronic effect of tert-butyldimethosilyl group was achieved. As a result, a variety of functionalized cyclpentanones have been easily prepared. And the new acceleration method of the Baeyer-Villiger reaction of polysubstituted cyclopentanones was found to give polysubstituted δ-lactones. These new reactions applied to efficient syntheses of Corey lactone, an important intermediate of prostagrandins, and lactone portion of antitumor marine antibiotics discodermolide.A new methodology for the asymmetric synthesis of β-hydroxy acid was developed. Dirhodium(II)-catalyzed C-H insertion of α-alkoxydiazoketone, which was prepared from primary alkyl halide and readily available chiral α-hydroxy acid, gave stereoselectively 2,5-cis-disubstituted 3(2H)-furanone. The furanone was converted to chiral β-hydroxy acid with high optical purity.

利用叔丁基二甲硅基的立体电子效应控制铑催化的α-重氮酮的C-H插入反应，实现了高化学和立体选择性.因此，已经容易地制备了各种官能化的环戊酮。并发现了一种新的加速多取代环戊酮Baeyer-Villiger反应生成多取代δ-内酯的方法。这些新反应适用于前列腺素重要中间体Corey内酯和抗肿瘤海洋抗生素discodermolide内酯部分的高效合成，为β-羟基酸的不对称合成开辟了一条新的方法。以α-烷氧基重氮酮为原料，采用二铑（II）催化C-H插入反应，立体选择性地合成了2，5-顺式二取代3（2 H）-呋喃酮。将呋喃酮转化为高光学纯度的手性β-羟基酸。

项目成果

Takayuki Yakura, Tomoko Kitano, Masazumi Ikeda, and Jun'ichi Uenishi: "Stereoselective synthesis of fully substituted δ-lactone ; the C1-C8 fragment of discodermolide"Heterocycles. 59. 347-358 (2003)

Takayuki Yakura、Tomoko Kitano、Masazumi Ikeda 和 Junichi Uenishi：“完全取代的 δ-内酯的立体选择性合成；discodermolide 的 C1-C8 片段”杂环。 59. 347-358 (2003)

Takayuki Yakura: "Chemo-and stereoselective dirhodium(II)-catalyzed C-H insertion reaction of 5, 6-dioxygenated 2-diazo-3-oxohexanoates : Synthesis of an optically active highly functionalized cyclopentane"Tetrahedron. 55. 7461-7470 (1999)

Takayuki Yakura：“化学和立体选择性二铑（II）催化的 5, 6-二氧化 2-重氮-3-氧代己酸酯的 C-H 插入反应：光学活性高功能化环戊烷的合成”四面体。

Takayuki Yakura: "Stereoselective synthesis of fully substituted δ-lactone ; the C1-C8 fragment of discodermolide"Heterocycles. 59. 347-358 (2003)

Takayuki Yakura：“完全取代的 δ-内酯的立体选择性合成；discodermolide 的 C1-C8 片段”Heterocycles 59. 347-358 (2003)。

Takayuki Yakura: "Stereoselective synthesis of fully substituted δ-lactone ; the C1-C8 fragment of discodermolide"Heterocycle. 59・1. 347-358 (2003)

Takayuki Yakura：“完全取代的 δ-内酯的立体选择性合成；discodermolide 的 C1-C8 片段”Heterocycle 59·1（2003）。

Takayuki Yakura: "Asymmetric synthesis of β-hydroxy acid via stereoselective dirhodium(II)-catalyzed C-H insertion of α-alkoxydiazoketone"Chem.Pharm.Bull.. 51・4. 471-473 (2003)

Takayuki Yakura：“通过立体选择性二铑(II)催化的α-烷氧基重氮酮的C-H插入来不对称合成β-羟基酸”Chem.Pharm.Bull.. 51・4(2003)。