A general synthetic method applicable to acyclic and cyclic polyamines was developed. The methodology was exemplified by systematical synthesis of twelve macromonocyclic polyamines, 1 ([17] N 4) through 12 ([35] N 8), composed of the combination of four natural polyamine segments, spermidine, spermine, thermine, and thermospermine. These twelve designed macrocycles are exhausted numbers of possible structures defined by three ...