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Synthesis of Natural Products Based on the Allene Intramolecuar Cycloaddition Stategy

基于丙二烯分子内环加成策略的天然产物合成

基本信息

批准号：
61870089
负责人：
NAYAKAWA Kenji
金额：
$ 4.1万
依托单位：
Kyushu University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research
财政年份：
1986
资助国家：
日本
起止时间：
1986 至 1987
项目状态：
已结题

项目摘要

The intramoleculat cycloadditions of allenes constitute the versatile methods for the stepreocontrolled synthesis of variously functionalized polycylic compounds. In paticular Diels-Alder reactions fully enjoyed the merits of the uique structure of allenes and proceed with extraordinary ease. On the basis of this allene intramolecular cycloaddition strategr, we have developed wvatious general systheric methods as follows.1. New polycycile Lactone Synthesis.We habe found that the allenyl ether undergoes the intramolecular Diels-Alder reaction with extraordinarty ease due to the favorable geomtry. The adducts thus obtained are easily converted into the correponing polycyclic lactones by bydratio-oxidation procedure. This method was successfully utilized in the synthesis of vasrious polycyclic lactones and spplied to the total syntersis of noreqsuiterpene lactone, (+-)platyphyllide.2. Furan Ring Transfer (FRT) Reaction.We habe developed a novel ring rtransfer reaction of furans to fused furans by virstue of a facile intramolecular Diels-Alder reaction of allenyl furfuryl ether and base-catalyzed ring opening of the resulting adduct. This method also opened the way to a new generation of syntherically versatial isobenzofurans.3. New indole Synthesis.We have developed a new versatile indole synthesis based on the intramolecular Diels-Alder of allenic dienamide and dehydrogenation of the adduct. By this method a variety of alkylated indoles were synthesized. A new class of pyrrolophenathridone alkalid, Hippadine, was also synthsized using this new methodology.

联烯的分子内环加成反应是分步控制合成各种功能化多环化合物的通用方法。特别是Diels-Alder反应充分利用了联烯独特结构的优点，进行起来异常容易。基于这种联烯分子内环加成策略，我们发展了以下几种通用合成方法.新的多环内酯的合成：我们发现丙二烯基醚由于具有良好的几何构型，可以非常容易地进行分子内Diels-Alder反应。所得加合物经氧化还原反应可转化为相应的多环内酯。该方法已成功应用于多种多环内酯的合成，并应用于降冰片烯内酯、（+-）桔梗内酯的全合成.呋喃环转移（FRT）反应：利用丙二烯基糠基醚的分子内Diels-Alder反应和碱催化开环反应，我们发展了一种新的呋喃环转移反应。该方法也为合成新一代手性异苯并呋喃开辟了道路。新的吲哚合成。我们开发了一种新的通用吲哚合成的基础上，分子内的狄尔斯-阿尔德的联烯二烯酰胺和脱氢的加合物。用此方法合成了一系列烷基化吲哚。用这种新方法对一类新的吡咯并菲啶酮生物碱Hippadine进行了结构鉴定。