Expected and unexpected products in half curcuminoid synthesis: crystal structures of but-3-en-2-ones and 3-methylcyclohex-2-enones

Abstract

The expected (E)-but-3-en-2-ones compounds I and II (half curcuminoids) were obtained by the Claisen–Schmidt reaction between aldehydes 3,4-dimethoxybenzaldehyde or 4-nitrobenzaldehyde with acetone. Concomitantly, 3-methylcyclohex-2-enones compounds III and IV arose from an un- expected reaction of but-3-en-2-ones in the cascade reaction of a Michael-type addition of a second molecule of acetone followed by Robinson annulation under strong basic conditions. Both enones exhibit the (E)-configuration, compound I displays s-trans conformation, whereas compound II exhibits conformational disorder as solid solution of s-cis and s-trans conformations. The related 3-methylcyclohex-2-enones exhibit envelope conformation. Compound III constitutes an example of the rarest case of racemic solid solution (pseudoracemate), where a lack of chiral discrimination with respect to the two enantiomers leads to an enantiomeric disorder of a racemic mixture with different occupancies at the reference site. Due to the lack of strong hydrogen-bond donors in all compounds, the crystal packing is mainly stabilized by weak intermolecular C-H···O interactions between the molecules. The present work provides a new perspective on the search for by-products normally overlooked in Claisen–Schmidt condensations.