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

Visible light promoted fluoroalkylation of hydrazones using 4‐perfluoropyridine sulfides as fluoroalkyl radical sources is described. The process can proceed in neutral and reductive modes delivering either hydrazones or hydrazines, respectively, depending on structure of starting substrates and reaction conditions. For the reductive process, ascorbic acid is used as a terminal reductant, which recycles the photocatalyst and serves as a source of hydrogen towards nitrogen‐centered radicals.

Catalyst-free visible-light-mediated exchange of two photoredox active groups, a 4-perfluoropyridinylthio group and an iodide group, attached to a fluorinated alkyl fragment is described. The reaction can be preparatively performed in both directions by appropriate choice of wavelength, solvent, and counterion. In the forward reaction, alkyl sulfide interacts with an iodide anion to give alkyl iodide and a thiolate anion, with the driving force provided by blue light (455 nm). In the backward process, fluorinated alkyl iodide interacts with the thiolate under violet light (400 nm). The reactions proceed through the formation of electron donor-acceptor (EDA) complexes, which were observed by UV/Vis absorption or NMR spectroscopies. Evidence of the sulfur-iodide interaction was supported by X-ray analysis.