Construction Of C-C Bonds Via C-H Bond Functionalization Of N-methyl Aromatic Amines And Decarbonylation Of Aliphatic Aldehydes Reaction

The method of C(sp3)-H bond functionalization is used to construct C-C bond,which is a challenging synthetic pathway.In recent years,many literatures have been reported that N-methyl aromatic amines are used to construct new C-C bond reactions which refers to the functionalization of ortho-N C(sp3)-H bond,but it has many shortcomings,such as application of metal salts,high temperature and high pressure conditions,which are not conducive to the creation of green chemistry.Therefore,it is necessary to develop a green and economical synthesis route to construct C-C bond.In addition,aliphatic aldehydes are often used as a source of alkyl radicals because of their own advantages,what's more,its applications in the construction of C-C bonds have attracted many attentions.Hence,this paper mainly includes the following two contents:1?this paper is reportd a method,which is about that using free-metal catalyzed C(sp3)-H bond functionalization of N-methyl aromatic amines and radical addition cyclization with acetylene esters to construct several new C-C bonds,and then to synthesize quinoline derivatives.The specific content is as follows: DCP(2.0 equiv,0.4 mmol)as oxidant,it promoted cheap and readily available N-methyl aromatic amines(0.2 mmol)to undergo Single Electron Transfer(SET)pathway,then which generated a free radical intermediate;Subsequently,free radical addition and cyclization reactions with alkynoates(0.4 mmol)were occurred;Finally,1,4-dihydroquinoline and pyrrole [1,2-a] quinoline compounds were synthesized.41 samples were synthesized by extensive and high efficiency substrate expansion.The structure of the target compounds were determined by single crystal X-ray,NMR,and HRMS.2?A cheap transition metal salt was uesd to catalyze ?-C(sp3)-C(sp2)bond functionalization of aliphatic aldehydes,and then to construct C-C bond.In this paper,readily available transition copper salts(10 mol%)were used as catalysts,aliphatic aldehydes as substrates(1.0 mmol),DTBP(2.0 equiv,2.0 mmol)as free radical initiator,which promoted aldehyde to be acyl radical,and then the acyl radical underwent decarbonylation to yield the alkyl radical;Subsequently,C(sp3)-C(sp2)bonds were formed via free radical addition and decarboxylation reaction with cinnamic acid derivatives(0.5 mmol);Finally,alkyl-substituted E-alkenes were synthesized.A total of 15 examples were synthesized.The structure of the target compounds were determined by single crystal X-ray,NMR,and HRMS.Figure [60] Table [8] Reference [116]...