Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
J Org Chem. 2009 Sep 18;74(18):6915-23. doi: 10.1021/jo900869k.
Nitrogen heterocycles can be prepared by performing ring-expansion reactions of gamma-silyloxy-gamma-lactams, which are available by the annulation reactions of allylic silanes. Nucleophilic substitution of the annulation products and subsequent translactamization of nitrogen-tethered gamma-lactams provide six-, seven-, and eight-membered ring lactams. An enantiomerically enriched delta-lactam formed from this method was elaborated to form the hydroxypiperidine core structure of the pseudodistomin alkaloids.
氮杂环可以通过γ-硅氧基-γ-内酰胺的环扩张反应来制备，而γ-硅氧基-γ-内酰胺可以通过烯丙基硅烷的环化反应得到。环化产物的亲核取代以及随后氮连接的γ-内酰胺的转内酰胺化反应提供了六元、七元和八元环内酰胺。从该方法形成的手性富集的δ-内酰胺被进一步修饰，形成了伪表鬼臼碱类生物碱的羟基哌啶核心结构。
