Formation of Aminocyclopentadienes from Silyldihydropyridines: Ring Contractions Driven by Anion Stabilization

Abstract

Highly functionalized aminocyclopentadienes can be formed through the rearrangement of anions generated from readily prepared 6-silyl-1,2-dihydropyridines by desilylation with fluoride.T he scope and generality of the reaction was defined, and diverse transformations were performed on the highly functionalized products.Amechanism and driving force for the rearrangement were identified from experiments and DFT calculations. Scheme 1. Reactionso fsilyl-substituted DHPs 3.