Multivalent Functionalization of Cyclodextrins by Photochemical Thiol‐Ene Addition Reaction

Abstract Cyclodextrins are among the most popular host compounds in supramolecular chemistry. In this paper we describe a versatile approach to the multivalent functionalization of cyclodextrins by using photochemical thiol‐alkene addition reactions (“thiol‐ene click chemistry”). Starting from cyclodextrins allylated at the 2‐OH, 3‐OH and/or 6‐OH positions, a range of thiols could be introduced in good to excellent yields. By using alkanethiols substituted with hydroxy, carboxylic acid, ester, protected amine, and tetraethyleneglycol groups, a broad variety of functionalized cyclodextrins was obtained. By using fluorinated alkanethiols, highly fluorinated cyclodextrins (up to 56 wt.‐% of fluorine) were obtained in excellent yield.