Amine-catalyzed tunable reactions of allenoates with dithioesters: Formal [4+2] and [2+2] cycloadditions for the synthesis of 2,3-dihydro-1,4-oxathiines and enantioenriched thietanes

Abstract

The chemoselective [4+2] vs. [2+2] cycloaddition between allenoates and dithioesters can be controlled by switching the nucleophilic amine catalyst. The two modes of cyclizations represent the first example of controllable and chemoselective annulations between allenoates and dienophiles catalyzed by amine. These cyclizations are useful in offering a divergent synthesis of sulfur-containing heterocycles. On the basis of this investigation, it can be realized that dithioesters with a vicinal electron-withdrawing group can react not only like a Michael acceptor but also as a ketone or imine.