Biomimetic direct hydroperoxidation of unactivated C(sp³)–H bonds enables effective functionalization of diverse types of natural products and/or drugs

Organic hydroperoxides are a class of biologically significant molecules that exist ubiquitously in nature. The ideal synthesis is direct hydroperoxidation of C(sp3)–H bonds, which remained a substantial challenge, particularly for the unactivated C(sp3)–H bonds. Inspired by the bio-catalysis of cyclooxygenase, a direct and site-selective photochemical hydroperoxidation of unactivated C(sp3)–H bonds was thus developed involving O2 as the oxidant and bromine radical as the catalyst. This method, demonstrated by plenty of substrates (63 examples) enables the late-stage functionalization of diverse types of natural products and/or drugs, such as terpenoids, amino acids, peptides, sugars and phosphonates.