Visible-light-induced direct hydrodifluoromethylation of alkenes with difluoromethyltriphenylphosphonium iodide salt

N-Heterocyclic Nitreniums Can Be Employed as Photoredox Catalysts for the Single-Electron Reduction of Aryl Halides

“…We have been interested in developing transition-metal-free visible-light-induced transformations . Given the Lewis acid character of NHN salts, we questioned whether they could perform photoredox catalysis to achieve the single-electron reduction of aryl halides (Figure C).…”

Charge Transfer Complex-Enabled Synthesis of (Hetero)arylated m-Carboranes from m-Carborane Phosphonium Salts

“…Using this strategy, they successfully carried out photoarylation/photoheteroarylation of iodocarboranes with aryl iodides or arenes (Figure A). , Despite these impressive advancements, the visible-light-induced arylation of carboranes remains relatively underexplored. Recently, our group discovered that phosphonium salts are capable of forming charge transfer complexes (CTCs) with proper electron donors to produce organic radical species under blue-light irradiation without the need of photocatalysts and transition metals (Figure B) . Building upon this finding, here we disclose the use of m -carborane phosphonium salts to form CTCs, resulting in the production of carbon-centered m -carboranyl radicals upon blue-light irradiation (Figure C) .…”

Recent Advances in Visible Light‐Mediated Radical Fluoro‐alkylation, ‐alkoxylation, ‐alkylthiolation, ‐alkylselenolation, and ‐alkylamination

“…In combination with various photocatalysts and electron-rich donors, 1,2-additions to unsaturated systems or subsequent rearrangements after addition can be accomplished (Scheme 5). Chen [34] and Xiao [35] showed the transition metal-free hydrodifluoromethylation of alkenes when utilizing blue or white light, respectively. In the protocol by Chen and coworkers, the iodide counteranion in 6 serves as a suitable electron-rich donor capable of the reductive generation of * CF 2 H. Further DFT calculations supported a σhole effect of the phosphonium cation contributing to the stability and photo-driven single electron transfer from iodide (I À ) to difluoromethylphosphonium ion ( + PPh 3 CF 2 H).…”

“…TMSCF 3 (34), the Ruppert-Prakash reagent, is an important, bench stable fluoroalkylating reagent usually utilized as a precursor for nucleophilic trifluoromethylation. [82] The expansion of this reactivity for radical trifluoromethylation would be a desirable feat to avoid gaseous reagents such as CF 3 Br (26) or CF 3 I (27).…”