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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

  • 摘要: 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*RhCl22(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) Å,b=8.66(3) Å,c=18.48(6) Å,b=93.71(5)°,V=2 664(14) Å3, Z=2, Dc=1.350×103 kg/m3, F(000) 1 124, R1=0.086 7,wR2=0.227 5。

     

    Abstract: 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*RhCl22 (0.005 mmol, mole fraction is 5%), NaOAc (0.16 mmol), AgOTf(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, 13C, COSY, HSQC and HMBC) and single-crystal structure. Resultsshowthat the crystallographic data forcompound3:space group:P21/n, a=16.68(5) Å, b=8.66(3) Å, c=18.48(6) Å, b=93.71(5)°, V=2 664(14) Å3, Z=2, Dc=1.350×103 kg/m3, F(000) 112 4, R1=0.086 7, wR2=0.227 5。

     

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