Abstract : New sulfide‐functionalized bambus[4]urils ((RS)8BU[4]) and bambus[6]urils ((RS)12BU[6]) have been synthesized through thiol‐ene click coupling reactions (TEC) of allylbambus[n]urils. Synthesis of BU[6] derivatives always requires the use of a template anion (iodide, chloride or bromide) which is enclosed in the cavity of BU[6]. We show that this anion influences the reactivity of bambus[6]urils. An encapsulated iodide makes allyl functions of allyl12BU[6] less reactive towards TEC and hydrogenation reactions in comparison to the corresponding chloride or bromide inclusion complexes. This is critical for the chemical reactivity of BU[6] and even more to determine their anion‐binding properties. We report a new, facile and fast method using AgSbF6 to prepare anion‐free BU[6]. NMR methods were used to estimate association constants of these new empty BU[6] with different anions. Quantum chemistry calculations were employed to rationalize the observed results. These new functionalized bambusuril scaffolds in alternate conformation could find applications as multivalent binders.
https://hal-cea.archives-ouvertes.fr/cea-01790936
Contributor : Serge Palacin
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Submitted on : Monday, May 14, 2018 - 10:54:28 AM
Last modification on : Thursday, March 7, 2019 - 3:34:14 PM
Pierre Heck, Djamille Azazna, Marine Lafosse, Jialan Wang, Julie Rivollier, et al.. Functionalization of Bambusurils by thiol-ene click reaction and new, facile method for the preparation of anion-free Bambus[6]urils. Chemistry - A European Journal, Wiley-VCH Verlag, 2018, 24, pp.10793 -10801. ⟨10.1002/chem.201801468⟩. ⟨cea-01790936⟩
