DIHYDROSTILBENES OF CANNABIS - SYNTHESIS OF CANNIPRENE
DIHYDROSTILBENES OF CANNABIS - SYNTHESIS OF CANNIPRENE
复制标题
DOI：
10.1039/p19820001467
复制
发表时间：
1982-01-01
期刊：
影响因子：
--
通讯作者：
JAMIESON, SV
中科院分区：
文献类型：
--
作者：
CROMBIE, L;JAMIESON, SV
卡尼普林是由苯酚-阴离子叶立德与苯基保护醛反应合成的。苯甲酰化，然后氢化和氢解所得的二苯乙烯，得到半苯甲酰化的联苯，该联苯转化为其O-二甲基丙基-2-炔基衍生物。半氢化、Claisen重排和脱苯甲酰化得到三苯丙烯。在第二次合成中，首先合成了预苯化(3-甲基-2-烯基化)和苯基保护的环-B部分，并通过Wittig反应转化为二苄基保护的二苯乙烯。丁醇中的钠在不影响戊烯基团的情况下，一步还原二苯乙烯并除去苯基：甲醇中的镁能够在不脱苄的情况下还原二苯乙烯。由异香兰素二甲基丙基-2-芳基醚合成异香兰素二甲基丙基-2-芳基醚的总收率为19%，适用于同位素标记。还考虑了使用对溴苯基醚和甲氧基乙氧基甲基醚作为合成三丙烯的基础。合成了其他与大麻天然产物相关的联苯基，并合成了由大麻烯衍生的甲基化色满。
Canniprene is synthesized via reaction of a phenolate-anion ylide with a benzyl-protected aldehyde. Benzoylation, followed by hydrogenation and hydrogenolysis of the resulting stilbene, leads to a half-benzoylated bibenzyl which is converted into its O-dimethylprop-2-ynyl derivative. Semi-hydrogenation, Claisen rearrangement, and debenzoylation gives canniprene. In a second synthesis the prenylated (3-methylbut-2-enylated) and benzyl-protected ring-B section is made first and converted by Wittig reaction into a dibenzyl-protected stilbene. The stilbene is reduced and the benzyl groups removed in 1 step, without affecting the prenyl group, by sodium in butanol: Mg in methanol is capable of stilbene reduction without debenzylation. This practical synthesis proceeds in 19% overall yield from the dimethylprop-2-ynyl ether of isovanillin and is applicable to isotope-labeling. The use of p-bromophenacyl ether and methoxyethoxymethyl ether protection as the basis for canniprene synthesis is also considered. Other bibenzyls relevant to the natural products of Cannabis were made and the methylated chroman derived from canniprene is also synthesized.