1,4-cis-diaminotetra(di)deoxyheptitols from tropilidene - A variable access to tropa-type heterocycles

Article abstract of DOI:10.1002/jlac.199719970727

The synthetic potential of the dianhydrocycloheptenepentols 3 and dianhydrocycloheptaneheptols 4 - ultimately available from tropilidene - as intermediates en route to 1,4-cis-diaminotetra(di)deoxyheptitols is studied. With standard bivalent N nucleophiles (methyl-, benzylamine, hydrazines) the regioselective installation of two (e.g. 9, 34) amino functions has to compete with the generation of variously functionalized tropa-type 8-azabicyclo[3.2.1]octanes (e.g. 29, 30, 35, 45, 47). With azide (N₃^-) as monovalent nucleophile in unsaturated diepoxides 3 twofold, nearly regiospecific substitution (7) - in competition with [3,3]-sigmatropic migration (S_N2′ substitution) -, in saturated diepoxides 4 regioselective monosubstitution (39) can be achieved. VCH Verlagsgesellschaft mbH, 1997.