Development of highly selective reactions and application to the synthesis of complex natural products.

高选择性反应的开发及其在复杂天然产物合成中的应用。

基本信息

批准号：
59430023
负责人：
YONEMITSU Osamu
金额：
$ 21.76万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1984
资助国家：
日本
起止时间：
1984 至 1986
项目状态：
已结题

项目摘要

Research programs on the synthesis of organic compounds with high value from readily available materials are now extremely important for the great future of our country having very poor natural resources. Development in the modern fine synthetic organic chemistry consisting of highly functional, regio, and stereoselective reactions helds the key to success in such programs.Recently, we planned to synthesize some representative macrolide and polyether antibiotics from sugars, especially most readily available D-glucose, by a common synthetic methodology consisting mainly of 1) synthesis of three contiguous chiral centers by cyclic or acyclic stereocontrolled introduction of substituents at C-3 and C-5 positions of D-glucose, 2) construction of new chiral centers with at least 10 : 1 stereoselction by use of highly stereoselective reactions, 3) selective use of benzyl-type protecting groups for hydroxy groups (MPM, DMPM) removable by DDQ oxidation.In our synthetic programs, the following results so far obtained. 1) Benzyl-type (Bn, MPM, DMPM) protecting groups selectively removable by DDQ oxidation or catalytic hydrogenolysis with Raney Ni were developed. 2) Stereoselective synthesis of substituted tetrahydrofurans and tetrahydropyrans by stereocontrolled acid-catalyzed cyclization. 3) Highly stereoselective synthesis of macrolide aglycons having complex structures such as methynolide, pikronolide, erythronolide A, and tylonolide from Dglucose as a chiral starting materials was completed. 4) Highly stereoselective synthesis of the polyether antibiotic salinomycin from D-glucose, D-mannitol, and L-lactic acid was achieved.

现在，关于材料可用材料具有很高价值的有机化合物的研究计划对于我们国家的自然资源非常差的伟大未来非常重要。现代精细合成有机化学的开发，包括高度功能，区域和立体选择反应，为这种程序成功的关键而言，我们计划通过从1个常见的合成方法中构成1 contripic oigation op op of 1 contripial op of 1 contripial op of 1 contripial op of 1 contripial op of 1）定型的D-葡萄糖的C-3和C-5位置的取代基的引入，2）通过使用高度立体选择性反应的使用至少10：1立体选择，3）选择性地使用苯甲基型保护组（ddmpm，dmpm）connection soytion soe connection，ddq your dd qin section in Cynection soviention soviestion in Cynection in Cynection in Cynection seytion in Cynection in Cynection in Cynection in Cynection in Cynection seyter in Contigation seyter in Conteriative your DDQ远获得了。 1）开发了通过DDQ氧化或用Raney Ni催化氢解的选择性去除的苄基型（BN，MPM，DMPM）。 2）通过立体控制的酸催化的环化化，立体选择性合成了四氢呋喃和四氢呋喃。 3）高度立体选择性合成具有复杂结构的大环内酯类化合物，例如甲基醇，氯硝基醇，erythronolide A和dglucose作为手性起始材料的tylonolide。 4）从D-葡萄糖，D-甘露醇和L-乳酸酸中，高度立体选择性合成了聚醚抗生素盐霉素。