Non-transition Metal Catalyzed N-alkylation Reaction Of Oxazolidinone/amine

N-Alkylated amines are highly valuable organic compounds in many research areas because of their utility in the preparation of natural products,pharmaceuticals,dyes,agrochemicals,and other fine chemicals.Therefore,it is not surprising that in spite of the existing methods,development of new versatile and efficient protocols for their synthesis is of continuing interest.Among various synthesis routes,the break of N-H bond and the introduction of new alkyl/alkene fragments were involved in these transformations.This paper mainly focused on the researche work about two types of reactions involving amines/amides,which are Bismuth-catalyzed amine hydrogenation and Petasis reaction.These two methods have been successfully developed to synthesize amines derivatives by using simple secondary amine/amides.Firstly,we discovered that Bismuth-catalyzed intermolecular hydroamination of aryl ethylene with oxazolidione in toluene.The reaction could achieve good regioselectivity hydrogenation at arylbenzyl-position,and the highest yield of 99%was obtained.After that,the reaction scope of aryl ethylene was investigated under the optimized reaction conditions.In the aspect of electron withdrawing aryl ethylene,the appropriate temperature and reaction time could improve the yield of the reaction.Secondly,we also found that bismuth-thiourea can co-catalyze the oxidation coupling reaction of alkyl boric acid and oxadizolone.In the presence of H₂O₂ as oxidation N-styrene oxanolanone was obtained as main product.The olefin could couple with oxazolidione at N-position without transition metal catalyst.Because of the limited time before graduation,The reaction conditions are remained to be optimized.Finally,a Petasis Reaction of 2-pyridinecarbaldehydes with various amines and4-substituted 1,2-oxaborol-2?5H?-ols was developed.In the presence of HCl,the reaction proceeded smoothly under very mild conditions and the corresponding desired products were obtained in medium to excellent yields.This method allows the access a wide range of amines adjacent to heteroaromatic rings,which might be useful compounds in medicinal and material chemistry.