TOTAL SYNTHESIS OF LONGIFOLENE
TOTAL SYNTHESIS OF LONGIFOLENE
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DOI：
10.1021/ja00775a044
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发表时间：
1972-01-01
影响因子：
15
通讯作者：
ISSER, SJ
中科院分区：
文献类型：
--
作者：
MCMURRY, JE;ISSER, SJ
报道了一条全合成长叶烯(1)的新途径。从威兰-米歇尔酮开始，构建酮环氧化物10，然后由碱环成三环酮醇11。二溴卡宾加成烯烃得到11，接着是银离子辅助溶剂裂解扩环，得到烯丙醇19。它被氧化并与二甲基铜锂处理，通过令人惊讶的还原过程生成酮醇23。将23还原为二醇，然后进行单甲基化和裂解，得到脱氢长烯苯酮（29），容易转化为长烯烯。
A new route to the total synthesis of longifolene (1) is reported. Starting from the Wieland-Miescher ketone, the keto epoxide 10is constructed and then cyclized by base to the tricyclic keto alcohol 11. Dibromo-carbene addition to the olefin derived from 11, followed by silver ion assisted solvolytic ring enlargement, gives the allylic alcohol 19. This is oxidized and treated with dimethylcopper lithium to generate ketol 23 by a surprising reductive process. Reduction of 23 to a diol followed by monomesylation and fragmentation gives dehydrolongi-camphenilone (29) which is easily converted to longifolene.