TOTAL SYNTHESIS OF (-)-ALLOARISTOTELINE, (-)-SERRATOLINE, AND (+)-ARISTOTELONE
TOTAL SYNTHESIS OF (-)-ALLOARISTOTELINE, (-)-SERRATOLINE, AND (+)-ARISTOTELONE
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DOI：
10.1021/jo00055a007
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发表时间：
1993-01-29
影响因子：
3.6
通讯作者：
HEATHCOCK, CH
中科院分区：
文献类型：
--
作者：
STOERMER, D;HEATHCOCK, CH
如方案IV中所概述的，制备了马兜铃生物碱（-）-别马兜铃碱（4）、（-）-锯齿碱（12）和（+）-马兜铃酮（13）。因此，通过Stevens的方法，通过Hg（NO3）2介导的Ritter反应将（1 S）-（-）-β-蒎烯（9）和3-吲哚基乙腈（10）偶联，然后还原所得亚胺，得到（+）-makomakine（11）。分子内Friedel-Crafts反应产生（+）-Aristoteline（3），其通过与氧和铂反应而被氧化。中间体氢过氧化物的还原递送生物碱12。碱催化骨架重排12得到生物碱13，用LiAlH 4还原得到仲醇14 a，b的混合物。将这些醇中的每一种用HCl在甲醇中处理得到（-）-别阿里斯特林（4）。
The Aristotelia alkaloids (-)-alloaristoteline (4), (-)-serratoline (12), and (+)-aristotelone (13) have been prepared as summarized in Scheme IV. Thus, via the method of Stevens, (1S)-(-)-beta-pinene (9) and 3-indolylacetonitrile (10) were coupled by a Hg(NO3)2-mediated Ritter reaction followed by reduction of the resulting imine to give (+)-makomakine (11). An intramolecular Friedel-Crafts reaction delivered (+)-aristoteline (3), which was oxidized by reaction with oxygen and platinum. Reduction of the intermediate hydroperoxide delivered alkaloid 12. Base-catalyzed skeletal rearrangement of 12 provided alkaloid 13, which was reduced with LiAlH4 to obtain a mixture of secondary alcohols, 14a,b. Treatment of each of these alcohols with HCI in methanol afforded (-)-alloaristoteline (4).