Department of Chemistry, Zhejiang University, 310027, Hangzhou, China.
Chemistry. 2023 Jun 27;29(36):e202300776. doi: 10.1002/chem.202300776. Epub 2023 May 8.
The incorporation of the privileged amino functionality is of paramount importance in organic synthesis. In contrast to the well-developed amination methods for alkenes, the dearomative amination of arenes is largely underexplored due to the inherently inert reactivity of arene π-bonds and selectivity challenges. Herein, we report an intermolecular dearomative aminofunctionalization via direct nucleophilic addition of simple amines to chromium-bound arenes. This multicomponent 1,2-amination/carbonylation reaction enables rapid access to complicated alicyclic compounds containing amino and amide functionalities from benzene derivatives under CO-gas-free conditions, which also represents the first application of nitrogen-based nucleophiles in η -coordination-induced arene dearomatizations.
在有机合成中，引入特权的氨基官能团至关重要。与烯烃的胺化方法相比，由于芳环π键的固有惰性反应性和选择性挑战，芳环的去芳构化胺化在很大程度上尚未得到充分探索。在此，我们报告了通过简单胺的直接亲核加成到铬键合芳环上的分子间去芳构化氨基官能化。这种多组分 1,2-胺化/羰基化反应能够在无 CO 气体条件下，从苯衍生物快速获得含有氨基和酰胺官能团的复杂脂环化合物，这也是氮基亲核试剂在 η-配位诱导的芳环去芳构化中的首次应用。
