The photocatalytic generation and trapping of alkyl radicals is a powerful synthetic tool in organic chemistry, but it remains underexplored in biological settings. Here, we present two photoredox…

Nearly all photochemical transformations known to date follow Kasha’s rule, implying that reactions occur only from the lowest electronically excited state of a given spin multiplicity due to the fast...

El investigador del Centro Singular de Investigación en Química Biológica y Materiales Moleculares (CiQUS) y catedrático de la Universidade de Santiago de Compostela (USC), José Luis Mascareñas Cid,

Z,Z,Z-triene: A novel method to facilitate rapid access to the otherwise inaccessible conjugated Z,Z,Z-triene motif is reported.

Radical processes involving bismuth hold great potential, but innovative strategies are required to control the reactivity of bismuth intermediates. Herein, we report a direct photochemical decarboxy...

The homogeneous catalytic functionalization of methane is extremely challenging due to the relative nonpolarity and high C–H bond strength of this hydrocarbon. Here, using catalytic quantities (10 mol...

Bioisosteric replacement is vital in drug discovery; however, substituting core ring structures is challenging. Now, a strategy that converts pyridines into benzonitriles, via N-oxidation, photochemic...

Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function as photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and the picosecond decay of electronically excited radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze important synthetic transformations where organic radicals have been proposed as photocatalysts, comparing their theoretical maximum excited state potentials with the potentials required for the observed photocatalytic reactivity. We summarize mechanistic studies of structurally similar photocatalysts indicating different reaction pathways for some catalytic systems, addressing cases where the proposed radical photocatalysts exceed their theoretical maximum reactivity. Additionally, we perform a kinetic analysis to explain the photoinduced electron transfer observed in excited radicals on subpicosecond time scales. We further rationalize the potential anti-Kasha reactivity from higher excited states with femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.

(−)-Cylindrocyclophane A is a 22-membered C2-symmetric [7.7]paracyclophane that bears bis-resorcinol functionality and six stereocenters. We report a synthetic strategy for (−)-cylindrocyclophane A th...

The catalytic formation of C–C bonds from aryl halides is a highly attractive but unexplored area in the emerging field of bismuth redox catalysis. We report a chemoselective bismuth-photocatalyzed a....