Acetate-Enabled Selective Electrochemical Deuterolysis of Propargylic Carbonates

Abstract

Deuterated compounds are becoming more important in drug discovery, mechanistic studies, and materials science, yet their selective syntheses remain challenging. Here we report a powerful nickel-electrocatalyzed deuteration platform that converts readily available propargylic carbonates into deuterated allenes using D2O as a cost-effective deuterium source with a very high selectivity. The reaction delivers a broad range of deuterated allenes, including 1,3-dialkyl variants, which are very common in natural allenes, with an excellent level of isotopic incorporation. We have also demonstrated the synthesis of a deuterated natural product analogue and programmable access to mono- and dideuterated allenes with deuterium installed at one defined position or two. Mechanistically, electroreduction generates the active Ni(0) catalyst that initiates the catalytic cycle, whereas the acetate anion promotes efficient deuterolysis.