Transition-Metal-Free, Selective Reductive Deuteration of Terminal Alkynes with Sodium Dispersions and EtOD-d1

Abstract

A transition-metal-free single electron transfer reaction has been developed for the synthesis of [D₃]-alkenes from terminal alkynes using sodium dispersions as the electron donor and EtOD-d₁ as the deuterium source. Both reagents are cost-effective and bench-stable. This practical method exhibits remarkable terminal alkyne selectivity and exclusive alkene selectivity. Excellent deuterium incorporations and yields were achieved across a broad range of terminal alkynes without olefin isomerization. Of note, this reaction is highly solvent dependent. n-Hexane provides unique enhancement to this reductive deuteration process.