Can hypervalent iodine(III) reagents be included in (supra)molecular containers? Karen de la Vega-Hernández, Marcos G. Suero*, Pablo Ballester* Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Spain The past decades witnessed a steep rise in the development of hypervalent iodine(III) reagents (HIRs) as versatile oxidants and electrophilic reagents in organic synthesis. 1 Key to the reactivity of HIRs is their unique structure, containing a linear and weak hypervalent bond -highly sensitive to the substitution pattern-, and the distinctive T-shape of λ 3 -iodanes; 2 hence, slight modifications of the structural features of HIRs have marked influences on the reaction outcomes. Studies on HIRs binding in molecular and supramolecular containers along with the potential impact on their reactivity are scarce. Capitalizing on the cationic character of HIRs, we decided to study the putative formation of inclusion/encapsulation complexes with molecular and supramolecular containers that are well-known to bind positively charged and electron-poor guests. In all cases, binding experiments were monitored using 1 H NMR spectroscopic titrations. The formation of inclusion complexes was further supported by the results of 1 H DOSY experiments. Whenever relevant, competitive displacements of the bound guests and control experiments were also performed. As a result, we disclosed the unprecedented inclusion of HIRs within different hosts in both organic and aqueous media. The impact of the formation of HIRs inclusion complexes on their typical reactivity and selectivity in bulk solution will be preliminarily assessed.
References 1. a) Allouche E. M. D.; Grinhagena, E.; Waser, J. Angew. Chem. Int. Ed. 2022 , 61 , e202112287. b) Mironova, I. A.; Noskov, D. M.; Yoshimura, A.; Yusubov, M. S.; Zhdankin, V. V. Molecules 2023 , 28 , 2136. 2. Yoshimura, A.; Zhdankin, V. V. Chem. Rev. 2016 , 116 , 3328−3435.
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