Tandem 1,2-sulfur migration and (aza)-Diels–Alder reaction of β-thio-α-diazoimines: rhodium catalyzed synthesis of (fused)-polyhydropyridines, and cyclohexenes

Abstract

Rhodium catalyzed synthesis of substituted tetrahydropyridines was accomplished from readily accessible thio-tethered N-sulfonyl-1,2,3-triazoles. The reaction involves tandem rhodium catalyzed 1,2-sulfur migration in β-thio-α-diazoimines, generated from thio-tethered N-sulfonyl-1,2,3-triazoles, to thio-substituted 1-azadiene and subsequent self aza-Diels–Alder reaction. Interestingly, the methodology was effectively extended to the synthesis of fused tetrahydropyridines, dihydropyridines and cyclohexenes through the in situ trapping of the intermediate, 1-azadiene, with various dienophiles such as enol ether, enamine, ketene S,S-acetal, alkyne, alkene and diene. Furthermore, the direct conversion of propargyl sulfides to (fused)-tetrahydropyridines was also achieved through the successful integration of copper and rhodium catalysts in one-pot.