Synthesis and Complexation Properties of Suitcase-Shaped Macrotricyclic and Butterfly-Shaped Macrobicyclic Polyether Ligands

Article abstract of DOI:10.1021/jo00044a040

Ten suitcase-shaped macrotricyclic polyethers (1-10) containing nitrogen and carbon bridgehead atoms have been synthesized.These new cage compounds were prepared by connecting together two hydroxymethyl-substituted or two secondary amine-containing butterfly-shaped macrobicyclic polyethers by means of linear bifunctional connecting groups.Intermediate bis(hydroxymethyl)-substituted butterfly-shaped macrobicyclic polyether 14 was prepared by treating N,N'-bis(2-hydroxyethyl)ethylenediaamine with 5-methylene-3,7-dioxane-1,9-diyl ditosylate to give bislariat 1,4-diaza-13-crown-4 (11) which was cyclized with 3-chloro-2-(chloromethyl)-1-propene followed by hydroboration.Intermediate bissecondary amine-containing butterfly-shaped macrobicyclic polyethers 18 and 19 were prepared by treating N,N'-bis(2-hydroxyethyl)ethylenediamine with 6-tosyl-3,9-dioxa-6-aza-1,11-undecanediyl ditosylate (33) to give N-tosyl-N',N"-bis(2-Hydroxyethyl)triaza-15-crown-5 (12).Lariat crown ether 12 was cyclized with 33 followed by reduction with LiAlH4 to give 18, or with 4-tosyl-4-aza-1,7-heptanediyl ditosylate (36 to give 19.Some of the suitcase-shaped macrotricycles interacted with various cations.One was selective for Pb(2+) ions and another interacted strongly with Hg(2+).A crystal structure for the 13-NaClO4 complex also is reported.