Abstract
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 O2 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 MnIV 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.