Development of Catalytic Asymmetric Careade Reaction and Its Application to Total Syntheses of Bioactive Compounds

催化不对称Careade反应的进展及其在生物活性化合物全合成中的应用

• 批准号: 13470466
• 负责人: IHARA Masataka
• 金额: $ 4.42万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 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/en/grant/KAKENHI-PROJECT-13470466/
• 关键词: Cascade Reaction; Asymmetric Synthesis; Stereo Chemistry; Transition Metal Catalysed Reaction; Bioactive Compounds; Intramolecular Double Michael Reaction; Intramolecular Michael-Aedol Reaction; Fixation of Carbon Dioxide; キラルアミン; ルイス酸; 連続反応; 多

Cascade reactions forming multiple bonds in a stereo-and regio-selective manner by one procedure is one of the most ideal process in organic synthesis. We have been studying constructions of polycyclic ring systems by using cascade reaction under four different conditions, ionic reaction, radical reaction, transition metal catalyzed reaction and furthermore pericyclic reaction. we have already developed two types of cascade reactions, which are useful for natural products synthesis. Thus, intramolecular double Michael reaction provides a ploycyclic compound fused to six membered ring possessing five stereogenic centers. On the other hand, the intramolecular Michael-aldol reaction constructs polycyclic ring systems fused to four membered ring having multiple stereogenic centers. Catalytic asymmetric reactions of these cascade reactions were extensively studied.Recently, we have developed a new type of palladium-catalyzed cascade reaction ; treatment of propalgyl carbonate with phenol in the presence of catalytic amount of zero valence palladium producing a cyclic carbonate. The reaction has been easily extended to asymmetric synthesis using (S)-BINAP with high enantio selectivity.

级联反应是有机合成中最理想的方法之一。我们在四种不同的条件下，利用级联反应，离子反应，自由基反应，过渡金属催化反应和周环反应，研究了多环体系的结构。我们已经开发了两种用于天然产物合成的级联反应。因此，分子内双迈克尔反应提供稠合到具有五个立体中心的六元环的多环化合物。另一方面，分子内的Michael-aldol反应构建了稠合到具有多个立体中心的四元环的多环体系。近年来，我们发展了一种新型的钯催化的级联反应：在催化量的零价钯存在下，丙炔醛碳酸酯与苯酚反应生成环状碳酸酯。该反应具有很高的对映选择性，可用于（S）-BINAP的不对称合成。

项目成果

井原 正隆 他5名: "Simple Construction of Bicyclo[4.3.0]nonane, Bicyclo[3.3.0]octane, and Related Benzo Derivatives by Palladium-Catalyzed Cycloalkenylation"Organic Letters. 4. 4293-4296 (2002)

Masataka Ihara 和其他 5 人：“通过钯催化环烯基化简单构建双环[4.3.0]壬烷、双环[3.3.0]辛烷和相关苯并衍生物”《有机快报》4. 4293-4296 (2002)。

井原 正隆 他2名: "Remarkable Control of Radical Cyclization Processes of Cyclic Enyne : Total Syntheses of (±)-Methyl Gummiferolate, (±)-Methyl7β-Hydroxykaurenoate, and (±)-Methyl 7-Oxokaurenoate and Formal Synthesis of (±)-Gibberellin A_<12> from a Common Synt

Masataka Ihara 和另外 2 人：“环烯炔自由基环化过程的显着控制：(±)-甲基胶基酚酸酯、(±)-甲基 7β-羟基贝壳杉烯酸酯和 (±)-甲基 7-氧代贝壳杉烯酸酯的全合成以及 (±)-甲基 7-氧代贝壳杉烯酸酯的正式合成)-赤霉素 A_<12> 来自常见合成体

井原 正隆 他2名: "Ruthenium-Catalyzed Ring Expansion Reaction of Allenylcyclobutanols"Tetrahedron Letters. 42・43. 3877-3880 (2001)

Masataka Ihara 等 2 人：“钌催化的烯基环丁醇的扩环反应”Tetrahedron Letters 42・43 (2001)。

井原 正隆 他1名: "Development of Palladium-Catalyzed Cycloalkenylation and its Application to Natural Product Synthesis"Synlett. 8. 1211-1222 (2002)

Masataka Ihara 等 1：“钯催化环烯基化的发展及其在天然产物合成中的应用”Synlett。8. 1211-1222 (2002)

井原 正隆 他6名: "Rhodacyanine Dyes as Antimalarials. 1. Preliminary Evaluation of Their Activity and Toxicity"Journal of Medicinal Chemistry. 45・5. 995-998 (2002)

Masataka Ihara等6人：“Rhodacyanine染料作为抗疟药。1.其活性和毒性的初步评估”药物化学杂志45・5（2002）。