Synthesis of chiral azamacrocycles using the bis(α-chloroacetamide)s derived from chiral 1,2-diphenylethylenediamine

Article abstract of DOI:10.1002/jhet.5570360204

Optically active diphenyl-substituted tetraaza-12-crown-4 diamide (10), tetraaza-15-crown-5 diamide (12), tetraaza-18-crown-6 diamide (11), and hexaaza-18-crown-6 diamide (9) ligands were prepared by treating the appropriate secondary diamines with the (R,R)- and (S,S)- forms of 1,2- bis(N-methyl-α-chloracetamido)-1,2diphenylethane (20). Macrocyclic diamides 9 and 10 were reduced to form the optically active diphenyl-substituted hexaaza-18-crown-6 (13) and tetraaza-12-crown-4 (14), respectively. Reduction of macrocyclic diamide ligands 11 and 12 gave a complex mixture of products from which the desired tetraaza-15-crown-5 and 18-crown-6 compounds could not be isolated. Dichloride 20 was prepared by treating the chiral forms of 1,2- diphenylethylenediamine with chloroacetic anhydride or chloroacetyl chloride. The crystal structures for the (R,R)-form of dichloride 20 and the (S,S)-forms of macrocycles 10 and 11 are reported.