Biogenetically orientated enantioselective syntheses of the bicyclic-ether
substructure of Azadirachtin and of the spirocyclohexenone building block f
or the Agelorines are communicated. In the first case the kinetic resolutio
n of a cyclopentenone starting material is exercised in a high pressure Die
ls-Alder cycloaddition and in the second case the cycloadduct of a prochira
l spirocyclohexadienone is used for the differentiation of enantiotopic gro
ups.