Selective methylene oxidation in α,β-unsaturated carbonyl natural products.

ABSTRACT: α,β-Unsaturated carbonyl groups-which feature conjugated C=C and C=O bonds-are common in bioactive compounds. Late-stage functionalization of these compounds could involve oxidation of methylene (2°) C-H bonds while leaving the C=C double bonds that are important for biological activity intact^1-3. Although catalytic systems have been developed for selective oxidation of methylenes in the presence of aromatics⁴ and N-heterocycles⁵, olefins remain a long-standing challenge. Here we show that replacing the carboxylic acid with a hydrogen bond donor solvent in sterically hindered manganese PDP ([N,N'-bis(2-pyridylmethyl)]-2,2'-bipyrrolidine) catalysts changes the active oxidant to one that accelerates electron-rich methylene oxidation and significantly slows ep

SUBMITTER: Ahn C 

PROVIDER: S-EPMC12616576 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature