Journal article
Pnictogen-bonding catalysis: brevetoxin-type polyether cyclizations.
- Gini A Department of Organic Chemistry , University of Geneva , Geneva , Switzerland . Email: stefan.matile@unige.ch ; http://www.unige.ch/sciences/chiorg/matile/ ; Tel: +41 22 379 6523.
- Paraja M Department of Organic Chemistry , University of Geneva , Geneva , Switzerland . Email: stefan.matile@unige.ch ; http://www.unige.ch/sciences/chiorg/matile/ ; Tel: +41 22 379 6523.
- Galmés B Department de Química , Universitat de les Illes Balears , Palma de Mallorca , Spain.
- Besnard C Department of Organic Chemistry , University of Geneva , Geneva , Switzerland . Email: stefan.matile@unige.ch ; http://www.unige.ch/sciences/chiorg/matile/ ; Tel: +41 22 379 6523.
- Poblador-Bahamonde AI Department of Organic Chemistry , University of Geneva , Geneva , Switzerland . Email: stefan.matile@unige.ch ; http://www.unige.ch/sciences/chiorg/matile/ ; Tel: +41 22 379 6523.
- Sakai N Department of Organic Chemistry , University of Geneva , Geneva , Switzerland . Email: stefan.matile@unige.ch ; http://www.unige.ch/sciences/chiorg/matile/ ; Tel: +41 22 379 6523.
- Frontera A Department de Química , Universitat de les Illes Balears , Palma de Mallorca , Spain.
- Matile S Department of Organic Chemistry , University of Geneva , Geneva , Switzerland . Email: stefan.matile@unige.ch ; http://www.unige.ch/sciences/chiorg/matile/ ; Tel: +41 22 379 6523.
- 2020-11-30
Published in:
- Chemical science. - 2020
English
Pnictogen-bond donors are attractive for use in catalysis because of deep σ holes, high multivalency, rich hypervalency, and chiral binding pockets. We here report natural product inspired epoxide-opening polyether cyclizations catalyzed by fluoroarylated Sb(v) > Sb(iii) > Bi > Sn > Ge. The distinctive characteristic found for pnictogen-bonding catalysis is the breaking of the Baldwin rules, that is selective endo cyclization into the trans-fused ladder oligomers known from the brevetoxins. Moreover, tris(3,4,5-trifluorophenyl)stibines and their hypervalent stiborane catecholates afford different anti-Baldwin stereoselectivity. Lewis (SbCl3), Brønsted (AcOH) and π acids fail to provide similar access to these forbidden rings. Like hydrogen-bonding catalysis differs from Brønsted acid catalysis, pnictogen-bonding catalysis thus emerges as the supramolecular counterpart of covalent Lewis acid catalysis.
- Language
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- English
- Open access status
- gold
- Identifiers
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- DOI 10.1039/d0sc02551h
- PMID 33250977
- Persistent URL
- https://sonar.ch/global/documents/233011
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