Divergent Michael/Aldol Cascades Under Semi-Aqueous Conditions: Synthesis of Cyclopenta- and Cycloheptannulated (Hetero)arenes

The synthesis of 3-acetoxyindanones and (hetero)arene-fused dihydrotropones was achieved via divergent annulation cascades. Under mild aqueous and basic conditions, α-substituted enone-aldehydes and 1,3-carbonyls undergo a Michael/aldol/hemiketalization/retro-aldol cascade for the formation of 3-acetoxyindanones possessing two contiguous stereogenic centers, one of which is an all-carbon quaternary center. On the other hand, the same enone-aldehydes generate new classes of fused-dihydrotropones upon reaction with 2,4-dioxobutanoates under merely the same reaction conditions via a Michael/aldol/lactonization/decarboxylation cascade.