Synthesis of 1,2-diaminoadamantane and chiral ligands derived from it

A new synthesis of racemic 1,2-diaminoadamantane was accomplished, its resolution into enantiomers through diastereomeric salts with l-tartaric acid was carried out, which gave individual (S)-enantiomer in 26% yield. It was reacted with carbon disulfide to obtain (S)-octahydro-3a,7:5,9-dimethanocycloocta[d]imidazole-2(3H)-thione, for which an enantiomeric excess of 96% was determined by HPLC. The absolute (S)-configuration was inferred from the results of quantum mechanical calculations of optical rotation. A number of N-donor ligands were synthesized based on (S)-1,2-diaminoadamantane. The catalytic activity of their complexes with CuII, MnIII, and NiII was studied on the model Henry, Michael, and epoxidation reactions.