Heterogeneous Metal‐Free Nitrogen and Phosphorus Co‐Doped Carbons for Acids Synthesis from Tertiary Alcohol via Oxidative Cleavage of C─C Bonds

Abstract The oxidative cleavage and functionalization of C─C bonds in tertiary alcohols have emerged as a prominent research focus in organic synthesis. However, the inherent kinetic inertness and thermodynamic stability of C─C bonds and the lack of Cα‐H present formidable obstacles to achieving it directly and selectively, particularly those employing metal‐free catalysts. Herein, we describe a general and efficient metal‐free N and P co‐doped porous carbon material that enables the synthesis of carboxylic acids from tertiary alcohols. A broad array of structurally distinct linear and cyclic tertiary alcohols can smoothly undergo cleavage of C─C bonds to obtain carboxylic acids using O 2 as the terminal oxidant and H 2 O as a green solvent. Remarkably, the catalyst retains its activity over five consecutive reaction cycles. Characterization and experiment results indicate that the introduction of P species can increase the specific surface area and create more defective sites, which might be beneficial to the improvement of catalytic activity. The method features exceptional functional group compatibility, economical and recyclable catalyst, and wide substrate applicability.