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Angew Chem Int Ed Engl. 2015 Oct 26;54(44):13007-11. doi: 10.1002/anie.201505628. Epub 2015 Sep 7.

Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis.

Author information

1
Department of Polymer Chemistry, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands).
2
Melville Laboratory for Polymer Synthesis, Department of Chemistry, Cambridge University, Lensfield Road, Cambridge CB2 1EW (UK).
3
Department of Chemistry, King's College London, Britannia House, 7 Trinity Street, London SE1 1DB (UK).
4
Melville Laboratory for Polymer Synthesis, Department of Chemistry, Cambridge University, Lensfield Road, Cambridge CB2 1EW (UK). oas23@cam.ac.uk.
5
Department of Polymer Chemistry, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen (The Netherlands). a.herrmann@rug.nl.

Abstract

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.

KEYWORDS:

Diels-Alder reaction; asymmetric catalysis; host-guest systems; macrocycles; supramolecular chemistry

PMID:
26383272
PMCID:
PMC4643185
DOI:
10.1002/anie.201505628
[Indexed for MEDLINE]
Free PMC Article

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