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Development of Synthetic Methodologies for Acyclic Organic Molecules Having Multi-Chiral Centers and Their Application to Natural Product Synthesis

多手性中心无环有机分子合成方法的发展及其在天然产物合成中的应用

基本信息

批准号：
12304042
负责人：
MIYASHITA Masaaki
金额：
$ 13.46万
依托单位：
Hokkaido University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2000
资助国家：
日本
起止时间：
2000 至 2002
项目状态：
已结题

项目摘要

Development of highly stereoselective synthetic methodologies for acyclic organic molecules having contiguous asymmetric centers is one of the important research projects in modern synthetic organic chemistry in context with the chiral synthesis of biologically and medicinally important compounds. This research project was carried out aiming at the development of highly stereoselective synthetic methodologies for acyclic organic molecules having contiguous asymmetric centers using stereospecific substitution reactions of epoxides as synthetic strategy .when this grant was provided.(1) The C2 selective alkyl and alkynyl substitution reactions of 2,3-epoxy alcohols by the use of organoaluminum ate complexes.(2) Novel and powerful reagent system for stereospecific alkylation-silylation reactions of epoxides.(3) A regio- and stereoselective a-methylation of γ, δ-epoxy-α, β-unsaturated esters with a Me_2Zn-CuCN reagent.(4) Stereospecific acyclic stereocontrol with double inversion of the configuration.(5) The C2 selective nucleophilic substitution reactions of 2,3-epoxy alcohols mediated by trialkyl borates.(6) Stereoselective total synthesis of PM Toxin A, a corn Host-Specific Pathotoxins.(7) Total Synthesis of Ingenol.(8) Stereoselective total synthesis of zincophorin, the unique ionophore antibiotic.

具有连续不对称中心的无环有机分子的高立体选择性合成方法的发展是现代有机合成化学中重要的研究课题之一，在生物和医学重要化合物的手性合成方面具有重要意义。该研究项目是在获得该资助时开展的，目的是利用环氧化物的立体选择性取代反应作为合成策略，开发具有连续不对称中心的无环有机分子的高度立体选择性合成方法。(1)利用有机铝配合物对2，3-环氧醇进行C2选择性烷基和炔基取代反应。(2)用于环氧化物的立体定向烷基化-硅烷化反应的新型强力试剂体系。(3)用Me_2 Zn-CuCN试剂对γ，δ-环氧-α，β-不饱和酯进行区域和立体选择性α-甲基化。(4)立体特异性无环立体控制与双重反转的配置。(5)硼酸三烷基酯介导的2，3-环氧醇的C2选择性亲核取代反应。(6)玉米寄主特异性毒素PM毒素A的立体选择性全合成(7)Ingenol的全合成。(8)独特的离子载体抗生素锌磷蛋白的立体选择性全合成。