Stereoselective Synthesis of Highly-Congested Tetralin-Fused Spirooxindoles with Hydroxyl Group: Net Oxygen Atom Induced Hydride Shift/cyclization Process.

Highly stereoselective synthesis of tetralin-fused spirooxindoles with two contiguous stereogenic centers. In the present reaction, not only [1,5]-hydride shift/cyclization process, but also replacemnt of nitrogen atom to oxygen atom ocurred smoothly to give target structure with hydroxy grop in good chemical yields with good to excellent diastereoselectivities (up to d.r. = >20:1). Investigation of the reaction mechanism suggested that this “atom-replacement” event ocurred via the iminium cation intermediates.