Medium-Ring Nitrogen Heterocycles through Migratory Ring Expansion of Metalated Ureas
Medium-Ring Nitrogen Heterocycles through Migratory Ring Expansion of Metalated Ureas
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通过金属化脲的迁移扩环制备中环氮杂环
DOI：
10.1002/ange.201605714
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发表时间：
2016
影响因子：
--
通讯作者：
Hall J
中科院分区：
文献类型：
--
作者：
Hall J
简单的苯并稠氮杂环(吲哚、四氢喹啉及其同系物)在N，N‘-二甲基亚丙基脲(DMPU)存在下，通过用二异丙胺锂(LDA)去质子化它们的苄基尿素衍生物来进行迁移环的扩张。这些反应的产物是苯二氮卓类、苯二氮杂环类和它们的同系物，环大小为8-12。这些反应可以容忍一系列取代基型式和类型，并且可以表现出对映体专一性或非对映选择性。在高效合成这些原本难以获得的中环氮杂环化合物的过程中，很快就会产生相当大的复杂性。
Simple benzo‐fused nitrogen heterocycles (indolines, tetrahydroquinolines, and their homologues) undergo migratory ring expansion through deprotonation of their benzylic urea derivatives with lithium diisopropylamide (LDA) in the presence of N,N′‐dimethylpropylideneurea (DMPU). The products of the reactions are benzodiazepines, benzodiazocines, and their homologues, with ring sizes of 8–12. The reactions tolerate a range of substituent patterns and types, and may exhibit enantiospecificity or diastereoselectivity. Considerable complexity is rapidly generated in an efficient synthesis of these otherwise difficult‐to‐obtain medium‐ring nitrogen heterocycles.