Synthesis of nitrogen and sulfur macrocycles with cis exogenous oxygen and sulfur donor atoms

摘要: A series of new N4 and N8 macrocycles has been prepared, that includes cis-exogenous O2, S2 S/O atoms to allow chelation a metal external the macrocyclic ring. We found thioamide units within were unstable attack by secondary amines thus alkylated precursors containing only tertiary could lead exogenous-S2 macrocycles. Cyclisation tetraamine with dimethyloxalate or dithiooxamide led both via 1 + 2 cyclisation reactions exogenous-O2 respectively. Alkylation preformed was explored alkyl substitution at amine nitrogens in ring, however synthesis these species overall lower yielding than using precursors. Thionation an exo-O2 macrocycle analogue Lawesson's Reagent formation analogous exogenous-O,S Related S2N2 prepared route but not be isolated free larger ring analogues.