Amos, Stephanie G. E.Cavalli, DianaLe Vaillant, FranckWaser, Jerome2021-10-092021-10-092021-10-092021-09-2110.1002/anie.202110257https://infoscience.epfl.ch/handle/20.500.14299/181945WOS:000697496900001Ethynylbenziodoxolones (EBXs) are commonly used as radical traps in photocatalytic alkynylations. Herein, we report that aryl-substituted EBX reagents can be directly activated by visible light irradiation. They act as both oxidants and radical traps, alleviating the need for a photocatalyst in several reported EBX-mediated processes, including decarboxylative and deboronative alkynylations, the oxyalkynylation of enamides and the C-H alkynylation of THF. Furthermore, the method could be applied to the synthesis of alkynylated quaternary centers from tertiary alcohols via stable oxalate salts and from tertiary amines via aryl imines. A photocatalytic process using 4CzIPN as an organic dye was also developed for the deoxyalkynylation of oxalates.Chemistry, MultidisciplinaryChemistryalkyneshypervalent iodinephotochemistryquaternary centerssynthetic methodscarboxylic-acidsdecarboxylative alkynylationphotoredox catalysisalcoholsradicalsfragmentationcascadesoxalatesalkenestext::journal::journal article::research article