Study On Aza-Diels-Alder Reaction And C-H Bond Functionalization Induced By Radical Cation Salts

A catalytic radical cation salt induced the C-H functionalization of glycinederivatives with styrenes, and the aza-Diels-Alder reaction of anilines with aldehydeswere studied, producing a series of subsitituted quinolines in high yields. Furthermore,we have preliminarily developed the C-H functionalization reaction between glycinederivatives and1,3-dicarbonyls under catalytic radical cation induced conditions,synthesizing a series of1,4-dihydropyridine derivatives were synthetized. The detailswere showed as follows:(1) A peroxy radical cation intermediate generated by the coupling between O2andcatalytic TBPA~+, which initiated C3sp-H functionalization of glycine derivatives withstyrenes, producing a series of quinolines. The proposed mechanism shows that aperoxyl radical cation, might be involved in the catalytic oxidation.(2) A tandem cyclization/aromatization of anilines and aldehydes was achievedunder catalytic radical cation salt induced conditions, producing a series of2,3-disubstituted quinolines in good yields. In this reaction, the in situ generatedimine tautomerizs to enamine, which act as a dienophile to participate the tandemcyclization, and further elimination of anilino group triggers the aromatization oftetrahydroquinolines, avoiding harsh conditions.(3) A C3sp-H functionalization of glycine derivatives with1,3-dicarbonyls wasachieved, using catalytic radical cation salts as initiator under O2. A series of1,4-dihydropyridines were synthesized in mediat yields. This method provided aconvenient approach to1,4-dihydropyridines, which have potentially pharmaceuticalactivities.