Irradiation of vinyl and aryl azides with visible light in the presence of Ru photocatalysts results in the formation of reactive nitrenes, which can undergo a variety of C–N bond-forming reactions. The ability to use low-energy visible light instead of UV in the photochemical activation of azides avoids competitive photodecomposition processes that have long been a significant limitation on the synthetic utility of these reactions.

Over the past decade, there has been a renewed interest in the use of transition metal polypyridyl complexes as photoredox catalysts for a variety of innovative synthetic applications. Many derivatives of these complexes are known, and the effect of ligand modifications on their efficacy as photoredox catalysts has been the subject of extensive, systematic investigation. However, the influence of the photocatalyst counteranion has received little attention, despite the fact that these complexes are generally cationic in nature. Herein, we demonstrate that counteranion effects exert a surprising, dramatic impact on the rate of a representative photocatalytic radical cation Diels-Alder reaction. A detailed analysis reveals that counteranion identity impacts multiple aspects of the reaction mechanism. Most notably, photocatalysts with more non-coordinating counteranions yield a more powerful triplet excited state oxidant and longer radical cation chain length. It is proposed that this counteranion effect arises from Coulombic ion-pair interactions between the counteranion and both the cationic photoredox catalyst and the radical cation intermediate, respectively. The comparatively slower rate of reaction with coordinating counteranions can be rescued by using hydrogen-bonding anion binders that attenuate deleterious ion-pairing interactions. These results demonstrate the importance of counteranion identity as a variable in the design and optimization of photoredox transformations and suggest a novel strategy for the optimization of organic reactions using this class of transition metal photocatalysts.

Azidoformates are interesting potential nitrene precursors, but their direct photochemical activation can result in competitive formation of aziridination and allylic amination products. Here, we show that visible light activated transition metal complexes can be triplet sensitizers that selectively produce aziridines via the spin-selective photogeneration of triplet nitrenes from azidoformates. This approach enables the aziridination of a wide range of alkenes and the formal oxyamination of enol ethers using the alkene as the limiting reagent. Preparative scale aziridinations can be easily achieved in flow.

α,β-Unsaturated 2-imidazolyl ketones undergo [2+2] cycloaddition with a variety of Michael acceptors upon irradiation with visible light in the presence of Ru(bpy)32+. Cleavage of the imidazolyl auxiliary from the cycloadducts affords cyclobutane carboxamides, esters, thioesters, and acids that would not be accessible from direct cycloaddition of the corresponding unsaturated carbonyl compounds.

An 18-step synthesis of the antibiotic (+)-pleuromutilin is disclosed. The key steps of the synthesis include a highly stereoselective SmI2-mediated cyclization to establish the eight-membered ring, and a stereospecific transannular [1,5]-hydrogen atom transfer to set the C10 stereocenter. This strategy was also used to prepare (+)-12-epi-pleuromutilin. The chemistry described here will enable efforts to prepare new mutilin antibiotics.