Asymmetric Total Synthesis of Chiral Molecules

手性分子的不对称全合成

• 批准号: 05234102
• 负责人: YONEMITSU Osamu
• 金额: $ 64.06万
• 依托单位: Okayama University of Science (1994-1995)Hokkaido University (1993)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05234102/
• 关键词: asymmetric total synthesis; organic natural product; optically active chiral compound; selective reaction; biologically active compound; multi-step synthesis; condensation reaction; protecting group

Asymmetric synthesis of complex chiral compounds such as useful natural products is one of important purposes of modern synthetic chemistry. This project "asymmetric total synthesis of chiral molecules" was carried out by about 20 synthetic chemists for three years beginning in 1993. Target molecules of this project, divided in four groups, are not only structurally complex compounds with many chiral centers and functional groups but also quite useful compounds with important biological activities and new functions : 1) Regulatory compounds of biological functions. 2) Chemical signal compounds. 3) Pharmacologically and physiologically active compounds. 4) Biologically active natural products produced in ultramicroquantity. During three years, we obtained many noteworthy results such as new synthetic methods of prostacyclines and prostaglandins, asymmetric synthesis and absolute configuration determination of various pheromons, computer-aided synthesis of enediyn compounds, hapten synthesis of ciguatoxin, synthesis of the crucial intermediate of taxol, asymmetric synthesis of tetracyclins, total synthesis of antitumor aplyronine A,lactone-ring synthesis of tedanolide, and total synthesis of hygrolidin.

不对称合成复杂的手性化合物，如有用的天然产物，是现代合成化学的重要目的之一。本课题“手性分子的不对称全合成”从1993年开始，由约20名合成化学家进行了三年的研究。本项目的目标分子分为四类，一类是结构复杂、具有许多手性中心和功能基团的化合物，一类是具有重要生物活性和新功能的化合物：1）具有生物功能的调节化合物。2)化学信号化合物3)药理学和生理学活性化合物。4)以超微量生产的具有生物活性的天然产物。三年来，我们在前列环素和前列腺素的合成新方法、各种信息素的不对称合成和绝对构型确定、烯二炔类化合物的计算机辅助合成、雪卡毒素的半抗原合成、紫杉醇关键中间体的合成、四环素的不对称合成、抗肿瘤药物阿克罗宁A的全合成、替丹明的内酯环合成、以及潮霉素的全合成。

项目成果

K. Yamada: "Total Synthesis of Aplyronine A, a Potent Antitumor Subatance of Marine Origin." J. Am. Chem. Soc.116. 7443-7444 (1994)

K. Yamada：“Aplyronine A 的全合成，一种来自海洋的有效抗肿瘤物质。”

K.Mori: "Pheromone Synthesis, CLXIII. Synthesis of (9Z,25S,26R,43Z)-25,26-Epoxy-9,43-henpenta-contadiene and Its Antipode." Liebigs Ann. Chem.695 (1994)

K.Mori：“信息素合成，CLXIII。(9Z,25S,26R,43Z)-25,26-环氧-9,43-henpenta-cont二烯及其对映体的合成。”

M. Hirama: "Enantio-Controlled Synthesis of the AB Ring Moiety of Ciguatoxin." Synlett. 1252-1254 (1995)

M. Hirama：“雪卡毒素 AB 环部分的对映体控制合成”。

S.Ikegami: "Enantioselective Intramolecular C-H Insertions of α-Diazo β-Keto Esters Catalyzed by Dirhodi(II) Tetrakis〔N-phthaloyl-(S)-phenylalanine〕." SYNLETT. 353 (1994)

S.Ikegami：“Dirhodi(II) Tetrakis〔N-邻苯二甲酰-(S)-苯丙氨酸〕催化的 α-重氮基 β-酮酯的对映选择性分子内 C-H 插入” SYNLETT。

Hashimoto, S.: "Enhancement of Enantioselectivity in Intramolecular C-H Insertion Reactions of α-Diazo β-Keto Esters Catalyzed by Chiral Dirhodium(II)Carboxylates." Tetrahedron Lett.34. 5109-5112 (1993)

Hashimoto, S.：“手性四铑 (II) 羧酸盐催化的 α-重氮基 β-酮酯分子内 C-H 插入反应的对映选择性增强”，5109-5112 (1993)。