Multiphoton tandem photoredox catalysis of [Ir(dFCFppy)(dtbbpy)] facilitating radical acylation reactions.

Photoredox catalytic radical acylation reactions, utilizing [Ir(dFCFppy)(dtbbpy)] (IrIII) as the photocatalyst and α-keto acids as the starting substrates, have recently emerged as an attractive strategy for preparing ketone derivatives. While there is consensus on the importance of detailed mechanistic insights to maximize the formation of desired products, efforts focused on uncovering the underlying elementary mechanisms of IrIII photocatalytic radical acylation reactions are still lacking. Herein, using time-resolved spectroscopy, we observed the efficient quenching of the triplet state, IrIII*, electron transfer from α-keto acids, resulting in the generatation of the reduced IrII. Subsequently, IrII rapidly transforms into a stable IrH species through protonation, with α-keto acid acting as a proton donor. Upon absorbing additional photon(s), IrH is expected to transform into IrH, involving further hydrogenation/protonation. Emission and Fourier transform infrared (FTIR) spectroscopy, together with global analysis, identify the character of IrH/IrH* and corroborate its contribution to representative radical acylation reactions (decarboxylative 1,4-addition of α-keto acids with Michael acceptors, decarboxylative coupling of α-keto acids with aryl halides, and decarboxylative cyclization of 2-alkenylarylisocyanides with α-keto acids), where IrH/IrH* serves as the key species to trigger the second photoredox cycle. These results elucidate the existence and generality of the tandem photoredox catalysis mechanism for IrIII photocatalytic radical acylation reactions, providing advanced insights into the mechanism of IrIII-based photoredox processes and potentially expanding their application in the design and development of new synthetic methodologies.