Electrocatalytic Deuteration of Halides with D2 O as the Deuterium Source over a Copper Nanowire Arrays Cathode.

Abstract

Precise deuterium incorporation with controllable deuterated sites is extremely desirable. Here, a facile and efficient electrocatalytic deuterodehalogenation of halides using D2 O as the deuteration reagent and copper nanowire arrays (Cu NWAs) electrochemically formed in situ as the cathode was demonstrated. A cross-coupling of carbon and deuterium free radicals might be involved for this ipso-selective deuteration. This method exhibited excellent chemoselectivity and high compatibility with the easily reducible functional groups (C=C, C≡C, C=O, C=N, C≡N). The C-H to C-D transformations were achieved with high yields and deuterium ratios through a one-pot halogenation-deuterodehalogenation process. Efficient deuteration of less-active bromide substrates, specific deuterium incorporation into top-selling pharmaceuticals, and oxidant-free paired anodic synthesis of high-value chemicals with low energy input highlighted the potential practicality.