铑(Ⅲ)催化碳氢键活化合成氮杂环衍生物

Rhodium(Ⅲ)-catalyzed C-H Activation for the Synthesis of N-containing Heterocyclic Compound

采用一种过渡金属铑催化的咪唑盐类底物与炔烃的插入反应,实现了氮杂环衍生物的高效合成:以[Cp*Rh Cl2]2(0.005 mmol,摩尔分数5%)作为催化剂,醋酸钠(0.16 mmol)作为碱,三氟甲基磺酸银(1.2 mmol)作为氧化剂,催化二溴咪唑盐化合物(1)(0.1 mmol)与二苯乙炔(2)(0.5 mmol)反应,以80%产率制备出目标咪唑盐化合物3。对目标化合物3通过核磁(1H,13C,COSY,HSQC及HMBC)、X射线单晶衍射进行了表征,结果表明:化合物3属于单斜晶系,空间群P21/n,晶体学参数:a=16.68(5)?,b=8.66(3)?,c=18.48(6)?,b=93.71(5)°,V=2 664(14)?3,Z=2,Dc=1.350×10~3kg/m^3,F(000)1 124,R_1=0.086 7,wR_2=0.227 5。

An efficient method for the synthesis of highly popular N-containing heterocyclic compound from imidazolium substrate and alkyne is described. Treatment of diphenylacetylene with diimidazolium in the presence of [Cp＊Rh Cl2]2（0.005 mmol,mole fraction is 5%）, Na OAc（0.16 mmol）, Ag OTf（1.2 mmol） as oxidizing agent catalyzing dibromo imidazole salt 1（0.1 mmol） and diphenylacetylene 2（0.5 mmol） led to compound 3 in 80%yield. The object molecule was characterized by NMR spectroscopy（^1H,^13 C,COSY,HSQC and HMBC） and single-crystal structure. Results show that the crystallographic data for compound 3：space group： P21/n, a = 16.68（5）A^°,b = 8.66（3） A^°,c = 18.48（6） A^°,b = 93.71（5）°,V = 2 664（14） A^°3, Z = 2, Dc =1.350 × 10^3kg/m^3, F（000） 112 4,R1= 0.086 7, wR2= 0.227 5.