The Chameleonic Nature of the Nitro Group Applied to a Base-Promoted Cascade Reaction To Afford Indane-Fused Dihydrofurans

We disclose a Michael/Conia-ene/SN2 cascade reaction for the synthesis of Indane-fused dihydrofurans from 1,3-dicarbonyl compounds and 2-alkynylnitrostyrenes promoted by potassium carbonate in DMSO at room temperature. In this reaction, the nitro group has a chameleonic role, first as an electron-withdrawing group for the Michael addition, then the nitronate behaves as a nucleophile, and finally, the allylic nitro acts as a leaving group. The product is obtained as a single diastereomer, affording up to 82% with 1,3-keto esters and 58% with 1,3-diketones. Furthermore, DFT calculations of the reaction mechanism explained the chemoselective addition of the nitronate over the enolate to the unactivated triple bond, with the enolate addition being highly endothermic.