A photoinduced SET process enables the direct B−H bond activation of NHC–boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this photoinduced reaction simply takes advantage of the beneficial redox potentials of NHC–boranes, thus obviating the need for extra radical initiators. The resulting NHC–boryl radical was used for the borylation of a wide range of α‐trifluoromethylalkenes and alkenes with diverse electronic and structural features, providing facile access to highly functionalized borylated molecules. Labeling and photoquenching experiments provide insight into the mechanism of this photoinduced SET pathway.

The first photoredox-catalyzed defluoroborylation of polyfluoroarenes with NHC-BH3 has been facilely achieved at room temperature via a single-electron-transfer (SET)/radical addition pathway. This new strategy makes full use of the advantage of photoredox catalysis to generate the key boryl radical via direct activation of a B–H bond. Good functional group tolerance and high regioselectivity offer this protocol incomparable advantages in preparing a wide array of valuable polyfluoroarylboron compounds. Moreover, both computational and experimental studies were performed to illustrate the reaction mechanism.

A photoinduced, phosphoranyl radical-mediated protocol for the direct N–O cleavage of strained cycloketone oximes via a polar/SET crossover process was developed for the first time. This visible-light-driven direct N–O activation mode for oxime offers beneficial features such as streamlined synthetic process and versatile photochemical reactivities. Consequently, the alkenes and α-trifluoromethyl alkenes with varied electronic and structural features acted as competent radical receptors in this protocol, enabling facile accesses to a range of elongated cyano and/or gem-difluoroalkene-bearing compounds.

A series of novel difluorinated 2‐hydroxyl‐substituted dihydroquinolones have been firstly synthesized via selectfluor‐triggered tandem cyclizations of 2‐aminoarylenaminones. This new approach could occur under mild reaction conditions, and features easy operation and scalability.

A practical and straightforward synthetic route to construct a variety of 3-CF/CF-containing chromones via photoredox catalysis was developed. This novel protocol features a visible-light-induced radical-triggered tandem cyclization.