Anti-Markovnikov hydrochlorination and hydronitrooxylation of ?-olefins via visible-light photocatalysis

Abstract Conventional hydrofunctionalization of ?-olefins with mineral acids proceeds Markovnikov selectivity to afford branched isomers. The direct formation linear constitutional isomers is challenging, yet anti-Markovnikov addition would be valuable for the synthesis commodity chemicals, such as primary alcohols, which are currently only accessible via stoichiometric redox reactions, a full equivalent waste both oxidant and reductant. Strategies that utilize radical intermediates have been demonstrated, but activated alkenes, use aqueous remains elusive. Here we present reactions hydrochloric nitric acid unactivated alkenes. transformation enabled by in situ generation photoredox-active ion pairs, derived from acridine acid, combined charge- phase-transfer catalyst. introduction hydrogen atom transfer catalyst us bypass challenging chain propagation originates high bond dissociation energy.