Inorganic Bases Enhanced Organocatalysis for Aerobic α‐Hydroxylation of Aliphatic Cycloketones

Abstract Due to the lack of approach for aerobic α‐hydroxylation of the inert α‐C(sp 3 )‐H in aliphatic cycloketones, here we attempt to activate it by the combination of 1,5,7‐triazabicyclo [4.4.0] dec‐5‐ene with inorganic bases at controlled basicity. Via kinetic experiments, the role of weak inorganic bases was unveiled to protect TBD from the keto acid byproducts. Furthermore, by the investigation of substrate scope and DFT calculations, we revealed that the alkyl‐substitution induced ring strain release in cycloketones dominated both the reactivity and selectivity. We assume these findings could benefit the synthesis route designs and method developments for inert C−H oxidations.