Structure assignment of aminoconduritols by 15N NMR correlation spectroscopy; synthesis of a positional isomer of 7-deoxypancratistatin

Abstract

A positional isomer of 7-deoxypancratistatin was synthesized in 12 steps from epoxyaziridines 4 and 5. An intermolecular opening of the aziridine rather than the epoxide in the early stages of the synthesis led to 13, which did not match the properties of tetraacetate 10 derived from 7-deoxypancratistatin. At no stage of the synthesis did standard NMR techniques, involving 1H–1H or 1H–13C coupling, prove adequate for the structure assignment. Unambiguous structure was assigned by 1H–15N correlation NMR spectroscopy as well as by the conversion of epoxide 11 to diol 29 synthesized independently by another route. Experimental and spectral details are reported for all new compounds.Key words: 15N NMR spectroscopy, iso-7-deoxypancratistatin, Lewis acid catalyzed intramolecuar opening of epoxides, aminoconduritols.