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Highly Efficient Supramolecular Catalysis by Endowing the Reaction Intermediate with Adaptive Reactivity
Author(s) -
Jiao Yang,
Tang Bohan,
Zhang Yucheng,
Xu JiangFei,
Wang Zhiqiang,
Zhang Xi
Publication year - 2018
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.201713351
Subject(s) - supramolecular chemistry , reactivity (psychology) , catalysis , supramolecular catalysis , chemistry , combinatorial chemistry , nanotechnology , materials science , organic chemistry , molecule , medicine , alternative medicine , pathology
A new strategy of highly efficient supramolecular catalysis is developed by endowing the reaction intermediate with adaptive reactivity. The supramolecular catalyst, prepared by host–guest complexation between 2,2,6,6‐tetramethylpiperidin‐1‐oxyl (TEMPO) and cucurbit[7]uril (CB[7]), was used for biphasic oxidation of alcohols. Cationic TEMPO + , the key intermediate, was stabilized by the electrostatic effect of CB[7] in aqueous phase, thus promoting the formation of TEMPO + and inhibiting side reactions. Moreover, through the migration into the organic phase, TEMPO + was separated from CB[7] and recovered the high reactivity to drive a fast oxidation of substrates. The adaptive reactivity of TEMPO + induced an integral optimization of the catalytic cycle and greatly improved the conversion of the reaction. This work highlights the unique advantages of dynamic noncovalent interactions on modulating the activity of reaction intermediates, which may open new horizons for supramolecular catalysis.