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Red Light–Blue Light Chromoselective C(sp<sup>2</sup>)–X Bond Activation by Organic Helicenium-Based Photocatalysis

Md Mubarak Hossain, Aslam C. Shaikh, Ramandeep Kaur, Thomas L. Gianetti

2024Journal of the American Chemical Society54 citationsDOI

Abstract

Chromoselective bond activation has been achieved in organic helicenium ( n Pr-DMQA + )-based photoredox catalysis. Consequently, control over chromoselective C(sp 2 )–X bond activation in multihalogenated aromatics has been demonstrated. n Pr-DMQA + can only initiate the halogen atom transfer (XAT) pathway under red light irradiation to activate low-energy-accessible C(sp 2 )–I bonds. In contrast, blue light irradiation initiates consecutive photoinduced electron transfer (conPET) to activate more challenging C(sp 2 )–Br bonds. Comparative reaction outcomes have been demonstrated in the α-arylation of cyclic ketones with red and blue lights. Furthermore, red-light-mediated selective C(sp 2 )–I bonds have been activated in iodobromoarenes to keep the bromo functional handle untouched. Finally, the strength of the chromoselective catalysis has been highlighted with two-fold functionalization using both photo-to-transition metal and photo-to-photocatalyzed transformations.

Topics & Concepts

ChemistryPhotocatalysisPhotochemistryCatalysisPhotoredox catalysisVisible spectrumIrradiationElectron transferBlue lightSurface modificationOrganic chemistryPhysical chemistryOpticsPhysicsNuclear physicsOptoelectronicsRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsSulfur-Based Synthesis Techniques
Red Light–Blue Light Chromoselective C(sp<sup>2</sup>)–X Bond Activation by Organic Helicenium-Based Photocatalysis | Litcius