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Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis
Author(s) -
Zheng Lifei,
Sonzini Silvia,
Ambarwati Masyitha,
Rosta Edina,
Scherman Oren A.,
Herrmann Andreas
Publication year - 2015
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.201505628
Subject(s) - nanoreactor , supramolecular chemistry , supramolecular catalysis , catalysis , chemistry , lewis acids and bases , macromolecule , amino acid , combinatorial chemistry , stereochemistry , molecule , organic chemistry , biochemistry
Chiral macromolecules have been widely used as synthetic pockets to mimic natural enzymes and promote asymmetric reactions. An achiral host, cucurbit[8]uril (CB[8]), was used for an asymmetric Lewis acid catalyzed Diels–Alder reaction. We achieved a remarkable increase in enantioselectivity and a large rate acceleration in the presence of the nanoreactor by using an amino acid as the chiral source. Mechanistic and computational studies revealed that both the amino acid–Cu 2+ complex and the dienophile substrate are included inside the macrocyclic host cavity, suggesting that contiguity and conformational constraints are fundamental to the catalytic process and rate enhancement. These results pave the way towards new studies on asymmetric reactions catalyzed in confined achiral cavities.