Brook Rearrangement as Trigger for Dearomatization Reaction: Synthesis of Non‐Aromatic N‐Heterocycles**

Abstract

AbstractThe [1,2]‐Brook rearrangement stands as a potent technique for constructing complex molecules. In this study, we showcase its power in the dearomatization of aromatic N‐heterocycles. Through a concise four‐step process that integrates lithiation, nucleophilic addition, Brook rearrangement and dearomatization reaction, we demonstrate a versatile strategy for generating diverse non‐aromatic N‐heterocycles which exhibit ambident reactivities. Various acyl silanes, halo‐pyridines, and quinolines have been explored within this context. The synthetic utility of this methodology is demonstrated through the construction of complex architectures.