Biomimetic total synthesis of (-)-erinacine E.
Biomimetic total synthesis of (-)-erinacine E.
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DOI：
10.1021/ja7102795
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发表时间：
2008-01
影响因子：
15
通讯作者：
Hideaki Watanabe;M. Nakada
中科院分区：
文献类型：
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作者：
Hideaki Watanabe;M. Nakada
采用收敛法合成了（-）-erinacine E（1）的对映体纯关键中间体。该合成中的关键步骤是由化合物内苯甲酰基的1，2-迁移驱动的分子内羟醛反应，该化合物经过合理设计以防止逆羟醛反应，从而成功提供了1的应变骨架。考虑到一个假定的生物合成中间体，纹状体A的结构，由C4'乙酰基驱动的分子内羟醛缩合反应可能参与1的生物合成。该酰基迁移性闭环反应可应用于其他应变分子的合成。
Biomimetic total synthesis of (−)-erinacine E (1) has been achieved starting from the enantiopure key intermediate, which was prepared via the convergent approach developed by us. The crucial step in this synthesis is an intramolecular aldol reaction driven by the 1,2-migration of a benzoyl group within a compound that was rationally designed to prevent the retro-aldol reaction, thereby successfully providing the strained skeleton of 1. Considering the structure of a putative biosynthetic intermediate, striatal A, the intramolecular aldol reaction driven by the C4‘ acetyl group could be involved in the biosynthesis of 1. This acyl group migratory ring-closing reaction could be applied to the synthesis of other strained molecules.