6-Oxodendrolasinolide的全合成  

Total Synthesis of 6-Oxodendrolasinolide

作　　者：李毅[1] 张涛[2] 李裕林[1] 

机构地区：[1]兰州大学有机化学研究所功能有机分子化学国家重点实验室,兰州730000 [2]杭州民生药业集团绍兴制药有限公司,绍兴312071

出　　处：《高等学校化学学报》2007年第7期1292-1296,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20072012)资助

摘　　要：以香叶醇(2)和异戊烯醇(5)为起始原料,经过12步反应,以5·6%的总收率完成了倍半萜内酯6-Oxodendrolasinolide(1)的全合成.其关键步骤包括乙烯基二噻烷(7)的负离子与烯丙基氯(4a)的区域选择性烷基化反应和Corey′s氧化内酯化反应.An efficient total synthesis of 6-oxodendrolasinolide （1）, a new farnesane-type sesquiterpene lactone, was described. The synthetic route was completed from geraniol 2 and 3-methylbut-2-en-l-ol （5） through twelve steps in 5.6% overall yield. The key steps were regioselective alkylation of the anion of vinyldithian 7 with allylic chloride 4a to generate compound 8, followed by hydrolyzation of the dithiane to afford compound 9. The reduction of enone 9 gave alcohol 10, which was protected as a p-methoxylbenzylether 11. Subsequently, tetrahydropyranyl protective group was removed and oxidized to give the key intermediate aldehyde 13. Then after Corey＇s oxidative lactionization reaction followed by deprotection of the PMB group compound 15 was formed, which underwent Dess-Martin oxidation to afford the title compound 1.

关 键 词：全合成 丁烯酸内酯 倍半萜 区域选择性烷基化 

分 类 号：O621.3[理学—有机化学]