Evidence for hydrogen-bond enhanced structural anomeric effects from the protonation of two aminals, 5-methyl-1,5,9-triazabicyclo-[7.3.1]tridecane and 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane

Abstract

The structure of the monoprotonated ion, 2, of 5-methyl-1,5,9-triazabicyclo[7.3.1]tridecane, 1, as a picrate shows an NMeH+ group engaged in a transannular hydrogen bond with one of the aminal nitrogen atoms and this, in turn, induces a small but measurable structural anomeric effect in the aminal functional group. Diprotonation of 1 in CF3CO2H yields an equilibrium mixture of two isomeric bicyclic dications which are interconverted via a monocyclic ion containing a H2C=N+ group and further protonation by CF3SO3H traps the iminium ion as a monocyclic trication. The structure of the monoprotonated ion, 4, of 1,4,8,11-tetraazatricyclo[9.3.1.1 4,8]hexadecane, 3, as a perchlorate shows the catio..