Department of Applied Chemistry, Kyung Hee University, Yongin 17104, Korea.
Department of Chemistry, Kangwon National University, Chuncheon 24341, Korea.
Org Lett. 2021 Nov 19;23(22):9006-9011. doi: 10.1021/acs.orglett.1c03549. Epub 2021 Nov 9.
Herein, we describe the valence tautomerizations of fused 1,4-diazepines, which are reconstructed to give pyrrole derivatives and HCN gas. Several factors that influence the equilibrium between each valence tautomer of an 8π-electron diazepine skeleton are demonstrated. On the basis of these mechanistic studies, a cascade strategy for the construction of diazepines followed by ring contraction is developed to afford aryl- or alkyl-substituted pyrrolo[1,2-]quinolines that are otherwise challenging to fabricate. In addition, further transformations of the obtained products highlight the advantages of the developed methodology.
本文描述了稠合 1,4-二氮杂环庚烷的价电子互变异构，这些互变异构会重排成吡咯衍生物和 HCN 气体。本文展示了影响每个 8π 电子二氮杂环庚烷骨架价电子互变异构体之间平衡的几个因素。基于这些机理研究，开发了一种稠合二氮杂环庚烷然后进行环收缩的级联策略，以获得芳基或烷基取代的吡咯并[1,2-]喹啉，否则这些化合物很难制备。此外，对获得的产物进行的进一步转化突出了所开发方法的优势。
