14- and 17-Membered Macrocycles Containing Amide, Amino, and Carbamate Groups in The Monocyclic Skeleton: An Accidental Byproduct Obtained from a Residue after Separation.

A 14-membered cyclic compound () containing amide, amino, and carbamate groups, which was serendipitously obtained in the oily residue after the separation of 4-benzyl-1,4,7,10-tetraazacyldododecane-2,6-dione () and 4,16-dibenzyl-1,4,7,10,13,16,19,22-octaazacyclo-tetracosane-2,6,14,18-tetraone (), is reported. The structure of is formally a CO insertion between positions 3 and 4 of the 12-membered ring in . The CO insertion was confirmed in the synthesis of diethyl 2,2'-(benzylazanediyl)diacetate () by the reaction of benzylamine with ethyl bromoacetate using KCO as the base. In addition, the selective synthesis of and ethyl -benzyl--((2-ethoxy-2-oxoethoxy)carbonyl)glycinate () and their kinetic behavior are reported. The reaction of with triethylenetetramine afforded a 17-membered macrocycle (), which was obtained in an 18% yield. Compounds and were prepared from and by introducing benzyl groups to improve their solubility in organic solvents. Titration experiments using H NMR showed that both and exhibit Li selectivity.