Tomažin Urša, Grošelj Uroš, Počkaj Marta, Požgan Franc, Štefane Bogdan, Svete Jurij
Faculty of Chemistry and Chemical Technology, University of Ljubljana , Večna pot 113, SI-1000 Ljubljana, Slovenia.
ACS Comb Sci. 2017 Jun 12;19(6):386-396. doi: 10.1021/acscombsci.7b00027. Epub 2017 Apr 13.
A highly modular synthetic method for the preparation of acacen-type ligands and their coordination compounds was developed. A series of 46 acacen-type ligands were synthesized by a combinatorial acid-catalyzed transamination between six primary diamines and eight enaminones. The bis-enaminone products were used as tetradentate ligands for coordination of copper(II), nickel(II), cobalt(II), and palladium(II). Dependence of the preferred E- or Z-configuration of the enaminone ligand on the α-substituent of the enaminone moiety in solution was determined by NMR and confirmed by X-ray diffraction. The copper(II) complexes were tested for their suitability as catalysts in 3 + 2 cycloaddition of azomethine imine to methyl propiolate.
开发了一种用于制备acacen型配体及其配合物的高度模块化合成方法。通过六种伯二胺与八种烯胺酮之间的组合酸催化转氨反应合成了一系列46种acacen型配体。双烯胺酮产物用作四齿配体，用于与铜（II）、镍（II）、钴（II）和钯（II）配位。通过核磁共振（NMR）确定了烯胺酮配体在溶液中优先的E-或Z-构型对烯胺酮部分α-取代基的依赖性，并通过X射线衍射得到证实。测试了铜（II）配合物作为催化剂用于甲亚胺叶立德与丙炔酸甲酯的3 + 2环加成反应的适用性。
