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Masaaki Iwata, Hiroyoshi Kuzuhara, Design and Synthesis of Macromonocyclic Polyamines Composed of Natural Methylene Arrays, Bulletin of the Chemical Society of Japan, Volume 62, Issue 1, January 1989, Pages 198–210, https://doi.org/10.1246/bcsj.62.198
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Abstract
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]N4) through 12 ([35]N8), 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 arbitrarily chosen criteria concerning with methylene chain arrays and nitrogen content (four to eight). The common elements of the structural characteristics were analyzed and were found to be reduced to readily available three classes of simple N,N′-ditosylalkanediamines derived from diamines and triamine. Nitrogen content was increased systematically through the reaction of N,N′-ditosylalkanediamine with one of three ω-phthalimidated electrophiles followed by regeneration of the same functionality at symmetrical both terminals as the starting materials via a series of transformation reaction, in excellent yields. Tractable formamide intermediate profits the facile synthesis of acyclic polyamines with long chains. Cyclization was achieved, under high dilution conditions, through the reaction of α,ω-bis(tosylamide) with α,ω-ditosylates in DMF in the presence of cesium carbonate. The cyclization occurred in practical synthetic yields even in the formation of multi-membered ring when the shorter electrophile and the longest α,ω-bis(tosylamide) reacted.
