Boosting Energy‐Transfer Processes via Dispersion Interactions

The generation of open‐shell intermediates under mild conditions has opened broad synthetic opportunities during this century. However, these reactive species often require a case specific and tailored tuning of experimental parameters in order to efficiently convert substrates into products. We report a general approach that can overcome these ubiquitous limitations for several visible‐light promoted energy‐transfer processes. The use of either naphthalene (5–20 equiv.) or simple binaphthyl derivatives (10–30 mol %) greatly increases their efficiency, giving rise to a new strategy for catalysis. The trend is consistent among different media, photocatalysts, light sources and substrates, allowing one to improve existing methods, to more easily optimize conditions for new ones, and, moreover, to disclose otherwise inaccessible reaction pathways. We present the generalized beneficial effect of naphthalene and its simple derivatives on energy‐transfer reactions. Increased reactions rates and higher yields are achieved for several reactivities, varying substrates, solvents, light sources and photocatalysts. The consistent trend is observed using molar excess of naphthalene or a catalytic amount of tailored bi‐naphthyl derivatives. These findings can be broadly used to improve existing methods as well as to shrink the efforts required to develop new ones.