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Tuneable Control of Organocatalytic Activity through Host–Guest Chemistry
Author(s) -
Li Guotai,
Trausel Fanny,
Helm Michelle P.,
Klemm Benjamin,
Brevé Tobias G.,
Rossum Susan A. P.,
Hartono Muhamad,
Gerlings Harm H. P. J.,
Lovrak Matija,
Esch Jan H.,
Eelkema Rienk
Publication year - 2021
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.202102227
Subject(s) - supramolecular chemistry , catalysis , chemistry , combinatorial chemistry , molecule , reaction mechanism , supramolecular catalysis , organocatalysis , kinetic control , organic chemistry , enantioselective synthesis
Dynamic regulation of chemical reactivity is important in many complex chemical reaction networks, such as cascade reactions and signal transduction processes. Signal responsive catalysts could play a crucial role in regulating these reaction pathways. Recently, supramolecular encapsulation was reported to regulate the activities of artificial catalysts. We present a host‐guest chemistry strategy to modulate the activity of commercially available synthetic organocatalysts. The molecular container cucurbit[7]uril was successfully applied to change the activity of four different organocatalysts and one initiator, enabling up‐ or down‐regulation of the reaction rates of four different classes of chemical reactions. In most cases CB[7] encapsulation results in catalyst inhibition, however in one case catalyst activation by binding to CB[7] was observed. The mechanism behind this unexpected behavior was explored by NMR binding studies and p K a measurements. The catalytic activity can be instantaneously switched during operation, by addition of either supramolecular host or competitive binding molecules, and the reaction rate can be predicted with a kinetic model. Overall, this signal responsive system proves a promising tool to control catalytic activity.