Nucleophilic Dearomatization of Activated Pyridines Using Vinyl Sulfoxonium Ylides: Application to the Synthesis of Bis-Heterocycles

A highly efficient method has been developed for synthesizing 4-dienyl dihydropyridines through the nucleophilic dearomatization of activated pyridines using vinyl sulfoxonium ylides. This reaction follows the sequence involving ylide addition to activated pyridine, [2,3]-sigmatropic rearrangement, and subsequent sulfenic acid elimination. The resulting 4-dienyl dihydropyridines are then used in the synthesis of highly substituted bis-heterocyles. Control experiments and quantum chemical calculations were conducted to elucidate the selectivity and the mechanistic pathway.