Synthesis of <i>ω</i> ‐Functionalized Carbonyls from Hydroperoxides and N‐Hydroxy Compounds: Mn‐Assisted Generation of <i>N</i> ‐Oxyl and C‐Radicals Followed by Their Cross‐Сoupling

ABSTRACT The manganese‐catalyzed method for the synthesis of ω‐functionalized ketones and esters from alicyclic hydroperoxides and N‐ hydroxy compounds has been discovered. The disclosed transformation proceeds via Mn(II)/Mn(III) catalytic cycle, which fulfills two key functions: the selective reduction of hydroperoxides to alkoxy radicals and oxidation of N‐ hydroxy compounds to N ‐oxyl radicals. The generated alkoxy radicals undergo β‐ scission to form primary alkyl radicals ( ω‐ C‐centered radicals), which subsequently engage in cross‐coupling with N‐ oxyl radicals. In most cases, this process affords two types of products: a C─O coupling product (major) and a C─N coupling product (minor) reflecting spin density localization within the N ‐oxyl radicals. Notably, the initial hydroperoxide serves a dual role, acting both as an oxidant for Mn(II) and as a precursor of the C‐centered radicals, thereby significantly enhancing atom‐economy. The developed approach is applicable to a broad range of hydroperoxides and N ‐hydroxy compounds and affords ω ‐functionalized compounds with overall yields of C─O and C─N coupling products up to 83%.