In-Catalyzed Transfer Hydrogenation and Regioselective Hydrogen–Deuterium Addition to the Olefins

A unique and valuable methodology is developed for the hydrogenation of aromatic as well as aliphatic 1,1-di- and trisubstituted alkenes. In the presence of catalytic InBr 3, readily available 1,3-benzodioxole and residual H 2 O present in the reaction mixture are utilized as a hydrogen gas surrogate and proved to be a practical source of deuterium incorporation into the olefins on either side by varying the source of the starting deuterated 1,3-benzodioxole or D 2 O. Experimental studies show the transfer of hydride from 1,3-benzodioxole to the carbocationic intermediate generated from the protonation of alkenes by the H 2 O–InBr 3 adduct remains the critical step.