首次报道了在四氢呋喃和甲苯的混合溶剂中,10 mol%的Ta2O5在103℃条件下催化不活泼溴代芳烃与芳酸进行Barbier-Grignard反应,“一锅法”制备三级醇的方法.获得了一系列具有不同取代基的三级醇,并得到了48%-87%的良好收率,同时讨论了底物空间位阻和电子效应对反应的影响,提出了Ta2O5催化反应的可能机理.
Carried out in THF-toluene at 103℃, the first one-pot Barbier-Grignard reaction to synthesize tertiary alcohols has been developed and systematically investigated using aromatic acids and unactivated aryl bromides in the presence of 10 mol% of Ta2O5. A wide range of substituted tertiary alcohols were obtained in moderate to good yields of 48%-87%. Steric and electronic effects of reactants on the reaction have been discussed. A possible mechanism catalyzed by Ta2O5 is proposed.