A transition-metal-free single electron transfer reaction has been developed for the synthesis of [D]-alkenes from terminal alkynes using sodium dispersions as the electron donor and EtOD- d 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.

A modified Bouveault-Blanc reduction has been developed for the synthesis of α,α-dideuterio alcohols from carboxylic acid esters. Sodium dispersions are used as the electron donor in this electron transfer reaction, and ethanol-d is employed as the deuterium source. This reaction uses stable, cheap, and commercially available reagents, is operationally simple, and results in excellent deuterium incorporation across a broad range of aliphatic esters, which provides an attractive alternative to reactions mediated by expensive pyrophoric alkali metal deuterides.