Synthesis Of ?-phospholactams And Lactones From Diazoarylmethylenediaryloxophosphine Oxides

4-Aryltetrahydroisoquinolin-3-ones compounds are bioactive and have good applications in medicinal chemistry as anti-inflammatory agents,antiobesity drugs and anti-tumor drugs.For their structural analogues,benzo-?-phospholactam has not been reported yet.In this dissertation,(diazo(aryl)methyl)diarylphosphine oxides were selected as the precursors of arylmethylideneoxophosphoranes(phosphenes)and prepared according to the reported method in literature.After a series of optimizations on reaction conditions and imine substrates,the reactions of methyleneoxophosphoranes with cyclic imines,dibenzo[b,f][1,4]oxazepines,were achieved under microwave irradiation to synthesize benzo-?-phospholactams in good yields.The reaction happened via a nucleophilic addition of the imines to methylideneoxophosphoranes followed by an intramolecular Friedel-Crafts alkylation and aromatization.Under the optimal reaction conditions,both the diazo substrates and imine substrates were extended,but only substituted dibenzo[b,f][1,4]oxazepines led to the corresponding products in good yields.Later,the reactions of methyleneoxophosphoranes with aldehydes and ketones under microwave irradiation were carried out.The results showed that methyleneoxophosphoranes reacted with substituted aromatic aldehydes and even trisubstituted aromatic aldehydes to synthesize benzo-?-phospholactones in moderate to good yields,but for heteroaromatic formaldehydes and aliphatic aldehydes,the yields were not good.And for ketones,the yields of phospholactones were lower,and the alkenic byproducts increased.Obviously,the reactions under microwave irradiation were better than the corresponding light-assisted reactions.In general,the reactions of(diazo(aryl)methyl)diarylphosphine oxides with imines,aldehydes,and ketones were realized for the synthesis of benzo-?-phospholactams and lactones.