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Endohedral Functionalized Cage as a Tool to Create Frustrated Lewis Pairs
Author(s) -
Yang Jian,
Chatelet Bastien,
Dufaud Véronique,
Hérault Damien,
MichaudChevallier Sabine,
Robert Vincent,
Dutasta JeanPierre,
Martinez Alexandre
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.201808291
Subject(s) - superbase , frustrated lewis pair , lewis acids and bases , catalysis , chemistry , substrate (aquarium) , combinatorial chemistry , computational chemistry , stereochemistry , organic chemistry , oceanography , geology
A frustrated Lewis pair (FLP) system was obtained by confinement of the Lewis base partner, a Verkade's superbase, in a molecular cavity. Whereas the model superbase lacking cavity displayed no catalytic activity in Morita–Baylis–Hillman (MBH) reactions, when associated to titanium (IV) chloride, the encaged superbase turns out to be an efficient catalyst under the same conditions. The crucial role of the endohedral functionalized cage on catalytic performance was further demonstrated by the fact that model superbases with bulky substituents were much less efficient to produce active catalysts, as well as by inhibition and substrate selection experiments. 31 P NMR spectroscopy and mass spectrometry experiments evidenced that no interaction between the Lewis acidic and basic partners occurred when the superbase was capped by a cycloveratrylene (CTV) unit, thus creating a true FLP active system.