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Switching on Supramolecular Catalysis via Cavity Mediation and Electrostatic Regulation
Author(s) -
Qiao Yupu,
Zhang Long,
Li Jia,
Lin Wei,
Wang Zhenqiang
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201606847
Subject(s) - supramolecular catalysis , aldehyde , knoevenagel condensation , reactivity (psychology) , substrate (aquarium) , chemistry , catalysis , supramolecular chemistry , divalent , selectivity , metal ions in aqueous solution , combinatorial chemistry , carboxylate , molecule , metal , photochemistry , stereochemistry , organic chemistry , medicine , alternative medicine , oceanography , pathology , geology
Synthetic supercontainers constructed from divalent metal ions, carboxylate linkers, and sulfonylcalix[4]arene‐based container precursors exhibit great promise as enzyme mimics that function in organic solvents. The capacity of these artificial hosts to catalyze Knoevenagel condensation can be switched on when the aldehyde substrate possesses a molecular size and shape matching the nanocavity of the supercontainers. In contrast, little reactivity is observed for other aldehydes that do not match the binding pocket. This substrate‐dependent catalytic selectivity is attributed to the Brønsted acidity of the metal‐bound water molecules located inside the nanocavity, which is amplified when the size/shape of the aldehyde substrate fits the binding cavity. The electrostatic environment of the binding cavity and the Brønsted acidity of the supercontainer can be further modulated using tetraalkylammonium‐based regulators, leading to higher reactivity for the otherwise unreactive aldehydes.