1,3-Aza-Brook Rearrangement of Aniline Derivatives: In Situ Generation of 3-Aminoaryne via 1,3-C-(sp2)-to-N Silyl Migration

)-to-N 1,3-aza-Brook rearrangement have been achieved, allowing access to diverse aniline derivatives. Through crossover experiments, we demonstrated the intramolecular mechanism of 1,3-C-to-N silyl transfer. To gain insight into the regioselectivity observed in the reactions, we performed density functional theory calculations. Finally, the method was applied to the synthesis of xylanigripones A in five linear steps in an overall yield of 30%.