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Functionalization of Bambusurils by a Thiol–Ene Click Reaction and a Facile Method for the Preparation of Anion‐Free Bambus[6]urils
Author(s) -
Azazna Djamille,
Lafosse Marine,
Rivollier Julie,
Wang Jialan,
Cheikh Imen Ben,
Meyer Michel,
Thuéry Pierre,
Dog JeanPierre,
Huber Gaspard,
Heck MariePierre
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801468
Subject(s) - bromide , iodide , click chemistry , ene reaction , reactivity (psychology) , chloride , thiol , chemistry , polymer chemistry , ion , surface modification , methyl iodide , inorganic chemistry , medicinal chemistry , organic chemistry , medicine , alternative medicine , pathology
Abstract Sulfide‐functionalized bambus[4]urils ((RS) 8 BU[4]) and bambus[6]urils ((RS) 12 BU[6]) were synthesized through thiol–ene click coupling reactions (TEC) of allylbambus[ n ]urils. Thiosugars were grafted to BU[4] and BU[6]. 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 allyl 12 BU[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 AgSbF 6 to prepare anion‐free BU[6]. NMR spectroscopic methods were used to estimate association constants of these new empty BU[6] with different anions. Quantum chemical calculations were employed to rationalize the observed results. These new functionalized bambusuril scaffolds in alternate conformations could find applications as multivalent binders.