Protection of the carbonyl groups in 1,2-indanedione: propellane versus acetal formation

The product resulting from the reaction between 1,2-indanedione and ethylene glycol under acidic catalysis is 2,5,7,10-tetraoxapropellane and not 1,2-dispirane as previously reported. Similar reactions also occur with 2-mercaptoethanol and 1,2-ethanedithiol, which form analogous propellanes and not corresponding thioacetals. This explains the difficulty of removing the protective groups under acidic conditions. These findings were corroborated by quantum chemical calculations. Under similar conditions, the longer-chain diol, 1,3-propyleneglycol and its thiol-analogue, 1,3-propanedithiol, form only mono-acetals, even when a 3-fold excess of the diol is applied. The nucleophilic attack, however, takes place at different positions: while propanedithiol forms the acetal at C-1, propylene glycol forms the acetal at C-2. (C) 2008 Elsevier Ltd. All rights reserved.