Synthesis of Chiral Ligands on the Basis of 1-(Adamantan-1-yl)ethane-1,2-diamine

The reduction of 1-(adamantan-1-yl)-2-azidoethan-1-one oxime with LiAlH 4 gave racemic 1-(adamantan-1-yl)ethane-1,2-diamine, which was resolved with l-tartaric acid. The individual enantiomer was obtained with a yield of 20% and derivatized into 4-(adamantan-1-yl)imidazolidine-2-thione. The absolute configuration of the derivatized diamine was established by X-ray diffraction analysis, and the enantiomeric excess (96%) was determined using HPLC. Diamine and diimine ligands were synthesized on the basis of racemic and chiral (1 S )-1-(adamantan-1-yl)ethane-1,2-diamine. The catalytic activity nickel(II), copper(II), and manganese(II) complexes were studied in model Michael, Henry, and epoxidation reactions.