Controlled Reactivity of Viologens in Alkaline Solutions Via Cucurbit[7]uril Complexation - Archive ouverte HAL
Journal Articles European Journal of Organic Chemistry Year : 2024

Controlled Reactivity of Viologens in Alkaline Solutions Via Cucurbit[7]uril Complexation

Abstract

Abstract A series of N ‐alkyl‐ and N ‐aryl‐viologens has been studied in alkaline solutions. In this work, we evaluated the deuteration rate of the viologens in D 2 O solutions of pH values ranging from 7.3 to 12.7. Kinetic experiments and computational calculations showed the high reactivity of H−C(2) bonds toward deprotonation of N ‐aryl‐pyridinium moieties compared to N ‐alkyl‐pyridinium moieties, even in hybrid N ‐aryl/ N ‐alkyl dissymmetric viologens. However this high H−C(2) reactivity in liquid phase contrasted with the proton fragmentation mechanism observed in the gas phase by mass spectrometry. The H/D exchange rate of viologens in very strong alkaline conditions could be significantly reduced using cucurbit[7]uril (CB[7]) as supramolecular protecting group. Ultimately, CB[7] inclusion led to a selective protection of H−C(2) group of N ‐aryl‐pyridinium of dissymmetric viologens, and induced a supramolecular regioselective deuteration.
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hal-04733006 , version 1 (11-10-2024)

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Axel Bossavit, Valérie Monnier, Didier Siri, Gabriel Canard, Didier Gigmes, et al.. Controlled Reactivity of Viologens in Alkaline Solutions Via Cucurbit[7]uril Complexation. European Journal of Organic Chemistry, 2024, 27 (31), pp.e202400404. ⟨10.1002/ejoc.202400404⟩. ⟨hal-04733006⟩
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