Thermocontrolled Radical Nucleophilicity vs Radicophilicity in Regiodivergent C–H Functionalization
Buddhadeb Pal, Prasenjit Mal
Abstract
The temperature-dependent switching behavior of the saccharin radical is demonstrated, enabling the regiodivergent C 3 –H and C 7 –H functionalization of quinoxalin-2(1 H )-ones. The saccharin radical was generated through N–Br bond cleavage in N -bromosaccharin (NBSA) and was observed to transition between radical and radicophile roles. At −10 °C, it was utilized as a radicophile, resulting in 100% C 3 -amination, while at +35 °C, it acted as a radical, leading to exclusive C 7 -bromination. Radical nucleophilicity was controlled by temperature modulation.
Topics & Concepts
ChemistryAminationNucleophileSurface modificationRadicalRegioselectivityCleavage (geology)Bond cleavageMedicinal chemistryStereochemistryPhotochemistryOrganic chemistryCatalysisPhysical chemistryGeotechnical engineeringFracture (geology)EngineeringRadical Photochemical ReactionsOxidative Organic Chemistry ReactionsSynthesis and Biological Evaluation