A Very Efficient Route toward the 4a-Methyltetrahydrofluorene Skeleton: Short Synthesis of (±)-Dichroanone and (±)-Taiwaniaquinone H
A Very Efficient Route toward the 4a-Methyltetrahydrofluorene Skeleton: Short Synthesis of (±)-Dichroanone and (±)-Taiwaniaquinone H
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DOI：
10.1021/jo900153y
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发表时间：
2009-05-01
影响因子：
3.6
通讯作者：
Fernandez, Antonio
中科院分区：
文献类型：
--
作者：
Alvarez-Manzaneda, Enrique;Chahboun, Rachid;Fernandez, Antonio
本文报道了一种合成具有4a-甲基四氢芴骨架的taiwaniaquinoids的新方法。关键步骤是芳基二烯的分子内Friedel-Crafts烷基化和亚甲二氧基的降解氧化;后一过程也可用于构建2-羟基-1，4-苯醌单元，这在天然产物中经常发现。利用这一新方法，从商品α-（11 a）或β-环柠檬醛（11b）合成了（+/-）-二色酮（7）（三步，总收率77%）和（+/-）-taiwaniaquinone H（6）（四步，总收率70%）。
A very expedient and efficient new route toward taiwaniaquinoids, bearing the 4a-methyltetrahydrofluorene skeleton, is reported. Key steps are the intramolecular Friedel-Crafts alkylation of an aryldiene and the degradative oxidation of a methylenedioxy group; the latter process could also be utilized for building the 2-hydroxy-1,4-benzoquinone unit, which is frequently found in natural products. Utilizing this new methodology, (+/-)-dichroanone (7) (three steps, 77% overall yield) and (+/-)-taiwaniaquinone H (6) (four steps, 70% overall yield) have been synthesized from commercial alpha- (11a) or beta-cyclocitral (11b).