Dirhodium Catalyzed Three Component Reaction Of α-diazo Esters,N，N-disubstituted Anilines And Allylic Compounds

Diaryl quaternary centers are important structural motifs found widely in natural products and pharmaceuticals.Therefore,it has important research significance in organic chemistry and medicinal sciences to develop methodologies for rapid synthesis of these significant units.Diazo compounds,as one of the most common carbene precursors,have been used extensively for various transition-metal-calalyzed reactions.Among them,multicomponent reactions（MCRs）involving diazo catalyzed by dirhodium can quickly and efficiently construct multiple chemical bonds from simple materials,which has the characteristics of atom and step economy,having attracted wide attention of chemists.However,the multicomponent reactions remain challenging in organic synthesis involving diazo with simple aromatic hydrocarbons as starting materials to directly construct diaryl quaternary carbon center.In this context,we have developed a highly efficient[Rh₂]/Xantphos-catalyzed three-component reaction ofα-diazo esters,N,N-disubstituted anilines and allylic compounds.The reaction is conducted at 50℃in CH₃CN using Rh₂（esp）₂（1.0 mol%）as the catalyst,Xantphos（1.5 mol%）as the ligand,and Cs₂CO₃（4 equiv）as the additive,affording a series of aniline derivatives bearing the diaryl allylic quaternary centers in good to excellent yields（41-99%）.This method has the characteristics of excellent chemical selectivity,broad substrate scope,good functional group tolerance and mild reaction conditions.In addition,when we extended this method to the late-stage functionalization of various bioactive molecules,the target products could also be obtained in moderate to high yields（53-99%）.Compared with the traditional methods of constructing the diaryl quaternary centers,this reaction is simple and convenient,and the functionalization of C（sp²）-H bond and allylic alkylation can be directly realized by a one-pot method employing a dirhodium catalyst,instead of adding additional catalysts to introduce the allylic structure.Moreover,to demonstrate the utility of this protocol,we also conducted a gram-scale reaction and derivatization research,both of which achieved excellent results.