Study On Dehydrogenation ?-functionalization Of N-alkyl Arylamines

?-Functionalized amines are extensively distributed in natural products,functional materials,pharmaceutical synthesis,agricultural products,therefore,the synthesis of?-functionalized amines is of significant importance in modern organic synthesis.Recently,the way to construct C-C bond through single-electron oxidation-induced cross-dehydrogenative coupling reaction has the advantages of high atomic economy,mild conditions,and meeting the requirements of green sustainable development.In this thesis,a base transition metal-catalyzed single electron oxidation strategy was used to achieve the dehydrogenative cross-coupling reactions between N-alkylarylamines and different nucleophiles?nitroalkanes,allylsulfones?,and produced a series of?-functionalized-N-alkylarylamines.The content includes the following two parts:In chapter 2,by using CuI/O₂?or TBHP?/TEMPO as a catalytic system,we have developed a dehydrogenative crossing coupling reaction between?hetero?arene-fused cyclic amines and nitroalkanes to achieve?-C?sp³?-H nitromethylation.The transformation proceeds with good substrate and functional group compatibility,high step and atom efficiency,and operational simplicity.And the obtained products are applicable for further transformation into the 2-aminoalkyl arene-fused cyclic amines via palladium catalyzed hydrogenation of the nitro group,which offers an important way in the preparation of synthetically useful 1,2-diamines.In chapter 3,a method allowing direct?-C?sp³?-H allylation of N-alkyaryamines with allyl sulfones has been developed in the presence of a[Ni]/TBHP system under N₂ protection.The catalytic transformation proceeds with good substrate and functional group compatibility,high step and atom efficiency,and operational simplicity.Moreover,the obtained products can be further applied for the elaboration of valuable structural motifs occurring in pharmaceuticall.In short,we have developed dehydrogenative crossing coupling reactions catalyzed by transition mental?Cu and Ni?between N-alkyl arylamine and different nucleophiles to achieve?-C?sp³?-H nitromethylation and allylation via single electron oxidation strategy,which provides an effective synthetic method for the structural modification of the?-position of N-alkylarylamines and enriches the connotation of organic synthesis methodology.