Annulation Reactions of Allene-Derived 1,3-Dipole with 3-Substituted-Chromones:  Unusual Recognition of 4π-Component in 3-(<i>N</i>-Aryliminomethyl)chromones through [4 + 3] Annulation

Abstract

All-carbon dipole derived by the interaction of triphenylphosphine with allenic ester is able to locate the polarized 2pi-component in 3-formylchromones through a regioselective [2 + 3] addition to the C2-C3 pi-bond, which is followed by deformylation leading to novel 3a,9a-dihydro-1-ethoxycarbonyl-1-cyclopenteno[5, 4-b]benzopyran-4-ones. On the contrary, the dipole recognizes azadiene in 3-(N-aryliminomethyl)chromones through [4 + 3] annulation and initially formed adducts undergo tandem rearrangements to afford novel N-aryl-2, 3-dihydro-4-ethoxycarbonylchromano[2,3-b]azepine-6-ones in good yield.