Heterogeneous Sodium‐Manganese Oxide Catalyzed Aerobic Oxidative Cleavage of 1,2‐Diols

The aerobic oxidative cleavage of 1,2‐diols using a heterogeneous catalyst only based on earth‐abundant metals manganese and sodium is reported for the first time. This reusable catalyst cleaves a variety of substrates into aldehydes or ketones with high selectivity. The reaction requires small catalytic loadings and is performed under mild conditions using ambient pressure O 2 or air as the oxidant while producing water as the only by‐product. Mechanistic investigations reveal a monodentate, two‐electron oxidative fragmentation process involving a Mn IV species. The eco‐friendly, innocuous catalyst is compatible with a wide range of functional groups and conditions, making it highly competitive with classical reagents, such as periodic acid or lead tetraacetate, as a preferred method for activated 1,2‐diols.