The Research On The Regioselectivering Opening Of N-tosylaziridines To Haloamines Using FeX₃?X=Br,Cl?

N-tosylaziridines,a kind of ternary heterocyclic compounds with bioactivity,exsites in kinds numerous of natural products which have antiviral property,antitumor properties and some other bioactivities.The high ring strain energy endows them with high reactivity.Reacted with different nucleophiles,N-tosylaziridines can be transformed to amines,amino acids,amino ethylmercaptan and other compounds.Thus,the ring opening of the aziridines have been attracted much attention of organic chemists.FeX3(X = Cl,Br)were found to be a very effective reagents for the regioselective ring openings of aziridines.The reaction conditions of cyclohexane N-tosylaziridines with FeCl3 were optimized by the halides type,solvent type,tempreture,amount of halides and solvent dosage,and the products were examined by TLC?IR?1H NMR?13C NMR?HRMS.The optimal reaction conditions:cyclohexane N-tosylaziridines 0.2 mmol as standard substrate,0.5 equiv of FeCl3,reaction temperature 25?,CH2Cl2 2.5 mL as solvent and up to 98%yield was provided.A variety of aromatic,aliphatic N-tosylaziridines and FeBr3 were extended under optimal reaction conditions.On the base of ring-opening reactions of aliphatic N-tosylaziridines with FeX3(X = Cl,Br),the scope of aromatic N-tosylaziridines was further researched.FeX3(X = Cl,Br)with as low as 40 mol%to aromatic N-tosylaziridines for regioselective ring-opening reaction to afford the corresponding ?-haloamines in good to excellent yields and with high regioselectivity under mild conditions because of aromatic N-tosylaziridines having higher activity than aliphatic N-tosylaziridines.There were 13 new products which were obtained from the ring openings of the aziridines,and were examined by 1H NMR?13C NMR?HRMS.Further application experiments of a series of Br-substituted organic compounds were studied.Some new functional groups can be smoothly introduced by nucleophilic substitution to their Br.The Br of the obtained product could be substituted easily with the nitro group(-NO2)of NaNO2 and optimal reaction conditions:standard substrate 0.2 mmol,1.5 equiv of NaNO2,reaction temperature 65?,DMSO 1.2 mL as solvent.The expected product was obtained in 55%yield.The advantages of nucleophilic ring opening reactions of aziridines with FeX3(X = Cl,Br):(1)FeX3(X = Cl,Br)was cheap and highly efficient;(2)simple experimental operation,mild reaction condition;(3)It has a very good yield and high regioselectivity.Therefore,this research has a great usefulness in synthetic chemistry.