Rhodium-catalyzed divergent dehydroxylation/alkenylation of hydroxyisoindolinones with vinylene carbonate.

Herein, a novel organic transformation involving rhodium-catalyzed divergent dehydroxylation/alkenylation of hydroxyisoindolinone with vinylene carbonate is reported, and a series of architecturally rigid and widely used spirolactams are obtained with excellent functional group tolerance and high selectivity. Remarkably, the promising vinylene carbonate reagent presents a distinct chemical reactivity as a vinyl-oxygen cyclic synthon and first transfers the C-H bond to spiroheterocycle scaffolds. Moreover, another chemoselectivity, direct dehydrogenative coupling with vinylene carbonate, is also presented. This protocol is compatible with green chemistry and only releases H 2 O and CO 2 as byproducts.