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Thermocontrolled Radical Nucleophilicity vs Radicophilicity in Regiodivergent C-H Functionalization
Buddhadeb Pal1, Prasenjit Mal1
1School of Chemical Sciences, National Institute of Science Education and Research (NISER) Bhubaneswar, An OCC of Homi Bhabha National Institute, PO Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha 752050, India.
Abstract:
The temperature-dependent switching behavior of the saccharin radical is demonstrated, enabling the regiodivergent C3-H and C7-H functionalization of quinoxalin-2(1H)-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% C3-amination, while at +35 °C, it acted as a radical, leading to exclusive C7-bromination. Radical nucleophilicity was controlled by temperature modulation.
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