Iron-Catalyzed Regioselective C═C Bond Migration and Reductive Deuteration.

We report a well-defined multifunctional iron catalyst, Cp*Fe(Ph2PN = C5H4N), that promotes the rearrangement of β,γ-unsaturated ketones, esters, and amides to their α,β-isomers, enabling regioselective C═C reductive deuteration. This iron-catalyzed protocol showcases the synthesis of a diverse range of α,β-dideuterated organic compounds, demonstrating broad substrate compatibility under mild conditions. Mechanism studies provide insights into the C═C bond relocation and cooperative D2 activation.