Sequential Oxygen Transfer via Oxidation of Arsine and Reduction of Arsine Oxide

Abstract Phosphine‐mediated reactions exploiting the oxophilicity of phosphorus have been extensively studied. However, the phosphine oxides generated in these reactions are often difficult to utilize in subsequent reactions because of their high stability. In this study, owing to their low oxophilicity, arsines were investigated as alternatives to phosphines. To demonstrate this concept, an arsa‐Appel reaction of benzyl alcohol was developed using arsines. The resulting benzyl bromide was further converted to benzaldehyde by the arsine oxides produced during the arsa‐Appel reaction. In this reaction system, oxygen atoms are transferred through the oxidation of arsine and subsequent reduction of arsine oxide.