Preparation of sixteen 3-hydroxy-4- and 7-hydroxy-1-hydrindanones and 3-hydroxy-4- and 8-hydroxy-1-hydroazulenones

3-Hydroxyoctahydro-4H-inden-4-ones and 7-hydroxyoctahydro- 1H-inden-1-ones (1, 2 and 3, 4, respectively), as well as the homologous 3-hydroxyoctahydro-4(1H)-azulenones (5, 6) and 8-hydroxyoctahydro-1(2H)-azulenones (7, 8), were prepared diastereoselectively either from the precursor alpha,beta-enones 9, 10, 11, and 12 or by an isoxazoline method. Unmasking of the isoxazolines 13i, 14i, and 14j with O-3 proved a more stereoselective process than hydrogenolysis. In many cases epimerization with 100 % completeness was observed on passing the epimerizable diastereomers once through a column filled with silica gel, the trans-fused hydrindanones thus in most cases furnishing the cis-fused epimers and the cis-fused hydroazulenones the trans forms. These results have been corroborated by AM1 theoretical computations, which indicate that the cis-fused epimers in these hydrindanone systems are more stable than the trans-fused variants, whereas the reverse was calculated for the hydroazulenone homologues. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007).