手性脱氢枞胺希夫碱铜配合物催化不对称Henry反应的研究

Catalyticability of chiral dehydroabietylamine schiff base copper(Ⅱ)complexes in asymmetric Henry reaction

合成了基于松香衍生物脱氢枞胺的光学纯手性希夫碱配体N-(2-亚甲基吡啶)脱氢枞胺(L)的铜配合物,以及铜配合物[Cu(L)2Cl]Cl(1)和[Cu(L)2Br]Br(2).研究了铜配合物催化苯甲醛和硝基甲烷的不对称Henry反应的活性,考察了金属盐的种类、配体/金属比例、溶剂、反应温度和时间及外加碱等条件对反应的影响.实验结果表明:在无须除氧和除湿的温和条件下,即时生成的CuCl2-L配合物作为催化剂的反应产率和选择性较高,配合物1和2没有催化活性.

The catalytic efficiency of in situ generated copper(Ⅱ)complexes of rosin-based chiral Schiff-base N-[(pyridin-2-ylmethylene)-imino]dehydroabietylamine)(L)and pre-prepared copper complexes[Cu(L)2 Cl]Cl(1)and[Cu(L)2 Br]Br(2)was estimated in the asymmetric Henry reaction of benzaldehyde and nitromethane.The effect of metal salts type,ligand/metal ratio,solvent,reaction temperature and time and base additive on the reaction were studied.The optimal catalyst was the in situ generated CuCl2-L in terms of yield and enantioselectivity under mild experimental conditions without air or moisture exclusion,however,complexes 1 and2 were found to be ineffective.The results suggest it is deserved to explore rosin derivatives in asymmetric catalysis field.