新型手性双二茂铁希呋碱亚胺配体的合成及其在不对称环丙烷化反应中的应用

Synthesis of Novel Chiral Bisferrocenylimino-phosphine Ligands and their Application in Ru(Ⅱ)-catalyzed Asymmetric Cyclopropanation

以手性二茂铁乙胺为手性前体分别与吡啶二醛和吡啶二酮进行希呋碱缩合反应,合成了两种二茂铁手性亚胺膦配体,并经元素分析,1HNMR,31PNMR等手段进行了表征.用这类化合物作为手性配体,研究了其金属Ru(II)配合物对苯乙烯与重氮乙酸乙酯的不对称环丙烷反应的催化作用,结果表明该类化合物的Ru(II)配合物具有很高的催化活性.

Novel chiral bisferrocenylimino-phosphine ligands were synthesized by Schiff-base condensation between (R)-1-[(S)-diphenylphosphinylferrocenyl]ethylamine and 2,6-diformylpyridine and 2,6-diacetopyridine, respectively. The ligands were characterized by elemental analysis, ()~1H NMR and ()^(31)P NMR. The pyridine containing donor ligands were proved to be efficient in Ru(Ⅱ)-catalyzed asymmetric cyclopropanation of styrene with ethyl diazoacetate. High activity and moderate enantioselectivity were obtained using 1,2-dichloroethane as solvent.