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.

Reductive dimerization of isatin and its derivatives can be regarded as a step-economical pathway to construct 3,3'-disubstituted bisoxindoles, which was unfortunately accompanied by severe direct reduction as well as low efficiency. A visible-light driven, photoredox-catalytic protocol was developed to readily furnish 3,3'-dihydroxy- (dl-, > 20:1 dr) and 3,3'-diamino-bisoxindoles (meso-, 3.5:1 to 5:1 dr) in moderate to good yields, successfully circumventing the common problem. Two vicinal quaternary carbon centers were effectively assembled under the irradiation of visible light.

A facile and diversified synthesis of functionalized CF-containing benzoxepine derivatives via photoredox catalysis was achieved in this work. This novel protocol features broad substrate scope, mild reaction conditions, operational simplicity, easy scale-up, and versatile derivatization, which would facilitate its practical and broad applications in the construction of valuable and synthetically challenging heterocycles.

O-Perfluoropyridin-4-yl group was first installed onto cycloketone oximes as a new electrophore, which was proven to be efficient iminyl radical precursors under photocatalytic and thermal conditions. A range of O-perfluoropyridin-4-yl oximes were successfully utilized in C­(sp2)–C­(sp3) bond formations of quinoxalin-2­(1H)-ones and alkenes, providing facile accesses to a range of functionalized alkylnitriles.