用反Diels-Alder反应合成天然产物(英文)

Natural Products Synthesis by Retro - Diels - Alder Reaction

天然产物全合成主要在于发展有效的方法以组成碳骨架和立体控制引入必须的官能团。本文利用刚性分子三环癸二烯酮(1)为原料,立体控制地引入取代基及官能团组成目标分子所需的碳骨架及官能团后进行反Diels-Alder反应释放出取代环戊烯酮,从而进一步合成目标分子克罗莫酸G-I 2,D-I 3,F 4,B 7,蚊皇识别信息素18,6-表蚊皇识别信息素19以及经30获得的32,后者是全合成大环内酯生物碱27的关键中间体。用酶催化反应不对称乙酰化内消旋二醇24c得光学活性单乙酯24d(81％产率,98.3％对映体过量值)。24d经过官能团转换可得(+)及(-)1,从(-)1用相似的反应合成了光学活性蚁皇识别信息素(18)。

Stereospecific introduction of functionalities and substituents on the cyclopentenone ring in the rigid molecule tricyclo[5. 2. 1. 02,6]decadineone 1 followed by Retro - Diels - Alder reaction produced the cyclopentenone derivatives 6,7,14,22 and 29, which were converted into chromomoric acid C-I2, D-I3, F4, B7, 18 invictolide and 6 - epiinvictolide 19 as well as a key intermediate 30 for further synthesis of macrocyclic pyrrolizidine alkaloid merenskine 27.