芳基铋芳胺化反应

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 Barton等于 1986 年报道了一类制备芳胺类化合物的温和方法[1],[2],即用芳基铋试剂与脂肪胺或芳胺在铜或二价铜盐的催化下常温搅拌即可高产率的生成目标芳胺类 化合物。

      此反应对脂肪胺,芳胺有很好的收率, 对于一些非活性胺也有很好的收率,如 吲哚 ,酰胺,脲,咪唑,磺酰胺等。有报道称用三乙胺或吡啶作碱可促进反应。此反应常用溶剂为二氯甲烷,常用催化剂为醋酸铜,常温下反应。

     芳基铋试剂的制备通常是卤代芳烃的格氏试剂和氯化铋交换得到。

芳基铋试剂的典型操作 

     Bromo-3-trifluoromethylbenzene (5.0 g, 0.0222 mol), dissolved in dry Et2O (100 mL) was added dropwise to a mixture of magnesium turnings (0.594 g, 0.0244 mol) and I2 (0.001 g) in Et2O in dry flask under N2 and a gentle reflux was maintained for 1 h. The reaction mixture was then cooled to 0 ℃and dry bismuth trichloride (3.50 g, 0.0111 mol) was added. After 10 min the mixture was warmed to reflux with stirring for 3 hrs.  Water was added and the organic phase was separated, washed with water, dried (MgSO4) and concentrated under reduced pressure. The residue was chromatographed on a silica gel column (eluent: hexane/EtOAc 95/5) to give compound as yellow oil; yield, 52% 。

芳基铋试剂芳胺化典型操作: 

     A slurry of amine, triarylbismuth (1-2 eq.), anhydrous Cu(OAc)2 (1-1.5 eq.), the tertiary amine (0.1-1.5 eq.) in methylene chloride (~2.5 mL/mmol of substrate) was stirred at room temperature for 6-48 hrs. The products were isolated by direct flash column chromatography of the crude reaction mixture on silica gel. The progress of reaction could be monitored by TLC as well as by the color change from the initial deep blue to turquoise green, with the concomitant precipitation of grayish Cu(I) salt. Additional amounts of Ar3Bi and Cu(OAc)2 could be added during the course of the reaction to ensure complete conversion of the substrate. 


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