The use of photoredox catalysis to generate reactive heteroatom-centered radicals was first explored in the 1990s. [Ru(bipy)] was found to catalyze the fragmentation of tosylphenylselenide to phenylselenolate anion and tosyl radical and that a radical chain propagation mechanism allowed the addition of tosyl radical and phenylseleno- radical across the double bond of electron rich alkyl vinyl ethers. Since phenylselenolate anion is readily oxidized to diphenyldiselenide, the low quantities of diphenyldiselenide observed was taken as an indication that photoredox-catalyzed fragmentation of tosylphenylselenide was only important as an initiation step, and that most of the reactivity was due to a radical chain process.
Heteroaromatic additions to olefins include multicomponent oxy- and aminotrifluoromethylation reactions. These reactions use Umemotos reagent, a sulfonium salt that serves as an electrophilic source of the trifluoromethyl group and that is precedented to react via a single-electron transfer pathway. Thus, single-electron reduction of Umemotos reagent releases trifluoromethyl radical, which adds to the reactive olefin. Subsequently, single-electron oxidation of the alkyl radical generated by this addition produces a cation which can be trapped by water, an alcohol, or a nitrile. In order to achieve high levels of regioselectivity, this reactivity has been explored mainly for styrenes, which are biased towards formation of the benzylic radical intermediate.
Hydrotrifluoromethylation of styrenes and aliphatic alkenes can be effected with a mesityl acridinium organic photoredox catalyst and Langlois' reagent as the source of CF radical. In this reaction, it was found that trifluoroethanol and substoichiometric amounts of an aromatic thiol, such as methyl thiosalicylate, employed in tandem served as the best source of hydrogen radical to complete the catalytic cycle.
Intramolecular hydroetherifications and hydroaminations proceed with anti-Markovnikov selectivity. One mechanism invokes the single-electron oxidation of the olefin, trapping the radical cation by a pendant hydroxyl or amine functional group, and quenching the resulting alkyl radical by H-atom transfer from a highly labile donor species. Extensions of this reactivity to intermolecular systems have resulted in i) a new synthetic route to complex tetrahydrofurans by a "polar-radical-crossover cycloaddition" (PRCC reaction) of an allylic alcohol with an olefin, and ii) the anti-Markovnikov addition of carboxylic acids to olefins.