Cargando…
Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis
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 la...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
WILEY-VCH Verlag
2015
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4643185/ https://www.ncbi.nlm.nih.gov/pubmed/26383272 http://dx.doi.org/10.1002/anie.201505628 |
_version_ | 1782400486055346176 |
---|---|
author | Zheng, Lifei Sonzini, Silvia Ambarwati, Masyitha Rosta, Edina Scherman, Oren A Herrmann, Andreas |
author_facet | Zheng, Lifei Sonzini, Silvia Ambarwati, Masyitha Rosta, Edina Scherman, Oren A Herrmann, Andreas |
author_sort | Zheng, Lifei |
collection | PubMed |
description | 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. |
format | Online Article Text |
id | pubmed-4643185 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | WILEY-VCH Verlag |
record_format | MEDLINE/PubMed |
spelling | pubmed-46431852015-11-18 Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis Zheng, Lifei Sonzini, Silvia Ambarwati, Masyitha Rosta, Edina Scherman, Oren A Herrmann, Andreas Angew Chem Int Ed Engl Communications 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. WILEY-VCH Verlag 2015-10-26 2015-09-07 /pmc/articles/PMC4643185/ /pubmed/26383272 http://dx.doi.org/10.1002/anie.201505628 Text en © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. https://creativecommons.org/licenses/by/4.0/ © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Zheng, Lifei Sonzini, Silvia Ambarwati, Masyitha Rosta, Edina Scherman, Oren A Herrmann, Andreas Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis |
title | Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis |
title_full | Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis |
title_fullStr | Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis |
title_full_unstemmed | Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis |
title_short | Turning Cucurbit[8]uril into a Supramolecular Nanoreactor for Asymmetric Catalysis |
title_sort | turning cucurbit[8]uril into a supramolecular nanoreactor for asymmetric catalysis |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4643185/ https://www.ncbi.nlm.nih.gov/pubmed/26383272 http://dx.doi.org/10.1002/anie.201505628 |
work_keys_str_mv | AT zhenglifei turningcucurbit8urilintoasupramolecularnanoreactorforasymmetriccatalysis AT sonzinisilvia turningcucurbit8urilintoasupramolecularnanoreactorforasymmetriccatalysis AT ambarwatimasyitha turningcucurbit8urilintoasupramolecularnanoreactorforasymmetriccatalysis AT rostaedina turningcucurbit8urilintoasupramolecularnanoreactorforasymmetriccatalysis AT schermanorena turningcucurbit8urilintoasupramolecularnanoreactorforasymmetriccatalysis AT herrmannandreas turningcucurbit8urilintoasupramolecularnanoreactorforasymmetriccatalysis |