SYNTHESIS OF ARISTOTELIA-TYPE ALKALOIDS .7. SYNTHESES OF (+1-)-SORELLINE, (+1-)-SERRATENONE, AND (+1-)-ARISTOTELIN-19-ONE
SYNTHESIS OF ARISTOTELIA-TYPE ALKALOIDS .7. SYNTHESES OF (+1-)-SORELLINE, (+1-)-SERRATENONE, AND (+1-)-ARISTOTELIN-19-ONE
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DOI：
10.1002/hlca.19910740204
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发表时间：
1991-01-01
影响因子：
1.8
通讯作者：
BORSCHBERG, HJ
中科院分区：
文献类型：
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作者：
BURKARD, S;BORSCHBERG, HJ
由吲哚保护的2-(吲哚-3-基)乙醛(5)与松油胺衍生物(+/-)-4缩合得到的亚胺在无水HCOOH中以51%的产率环化成19-取代的霍巴汀衍生物(+/-)-20。这一关键中间体进一步精制成吲哚生物碱(+/-)-蛇床子酮((+/-)-22)和(+/-)-茶碱((+/-)-29)。在这些研究过程中，发现了一种新的重排：Lewis酸催化的芳磺酰基从吲哚N原子到苯环的1，3-迁移。由于发现合成的(+/-)-马兜铃素-19-酮((+/-)34)具有与马兜铃素完全不同的光谱性质，马兜铃素是一种代谢物，其结构最近被提出，导致对后者的结构进行了修订。
The imine obtained by condensing indole-protected 2-(indol-3-yl)acetaldehyde (5) with the terpinylamine derivative (+/-)-4 was cyclized in 51% yield to the 19-substituted hobartine derivative (+/-)-20 upon exposure to anhydrous HCOOH. This pivotal intermediate was further elaborated into the indole alkaloids (+/-)-serratenone ((+/-)-22) and (+/-)-soreline ((+/-)-29). In the course of these investigations, a novel rearrangement was uncovered: a Lewis acid-catalyzed 1,3-migration of an arylsulfonyl group from the indole N-atom into the benzene ring. The discovery that synthetic (+/-)-aristotelin-19-one ((+/-)34) has decidedly different spectroscopic properties than aristolasicone, a metabolite for which the structure has been recently proposed, led to a revision of the structure of the latter.