American Chemical Society
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Highly Diastereoselective One-Pot Synthesis of Spiro{cyclopenta[a]indene-2,2‘-indene}diones from 1-Indanones and Aromatic Aldehydes

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posted on 2006-04-28, 00:00 authored by Pelayo Camps, Luis R. Domingo, Xavier Formosa, Carles Galdeano, Diana González, Diego Muñoz-Torrero, Sílvia Segalés, Mercè Font-Bardia, Xavier Solans
Treatment of 1-indanones with aromatic aldehydes and NaOEt in THF affords complex spiropolycyclic compounds through a four-component reaction in which two molecules of each starting compound are combined with formation of four new carbon−carbon bonds, leading to the elaboration of a new five-membered ring that bears five contiguous stereogenic centers with a well-defined relative configuration. Different amounts of a minor epimer of the main product are also formed. The presence of methoxy substituents in the indanone component and the use of aldehydes derived from π-excedent heterocycles make the dimerization step a slower transformation. In these cases, better yields of spirodimers are obtained starting from the preformed enones. The reaction seems to take place by cross-aldol condensation, dehydration, and dimerization of the thus formed enones. The molecular mechanism of the dimerization reaction of enone 5g has been studied using DFT methods at the B3LYP/6-31G* level. The dimerization takes place through a process involving a Michael addition of a carbanion, obtained by deprotonation of 5g at the 3-position, to a second molecule of 5g, followed by an intramolecular Michael addition in the corresponding intermediate. The final protonation of the resulting anion accounts for the formation of the cis-fused pentacyclic system.