Dyotropic Rearrangement of β‐Lactams: Reaction Development, Mechanistic Study, and Application to the Total Syntheses of Tricyclic Marine Alkaloids

作者：Yun‐Shan Li, Jingyang Zhang, Yi Chen, Jiahua Pang, Yuejie Chen, Yefeng Tang · 发表于：Angewandte Chemie International Edition · 年份：2024 · DOI：10.1002/anie.202414985 · 被引用次数：10 · 研究领域：Synthesis of β-Lactam Compounds、Synthesis and Biological Activity、Asymmetric Synthesis and Catalysis

An unprecedented dyotropic rearrangement of β-lactams has been developed, which provides an enabling tool for the synthesis of structurally diverse γ-butyrolactams. Unlike the well-established dyotropic rearrangements of β-lactones, the present reaction probably proceeds through a dual-activation mode, and thus displays unusual reactivity and chemoselectivity. The combined computational and experimental results suggest that the dyotropic rearrangement of β-lactams may proceed through different mechanisms depending on the nature of migrating groups (H, alkyl, or aryl). Hinging on a chemoselective H-migration dyotropic rearrangement of β-lactams, we have completed the divergent synthesis of tricyclic marine alkaloids (-)-lepadiformine A, (+)-cylindricine C, and (-)-fasicularin within 11-12 longest linear steps.