en
Scientific article
Open access
English

Pnictogen-bonding catalysis: brevetoxin-type polyether cyclizations

Published inChemical Science, vol. 11, no. 27, p. 7086-7091
Publication date2020
Abstract

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.

Research group
Citation (ISO format)
GINI, Andrea et al. Pnictogen-bonding catalysis: brevetoxin-type polyether cyclizations. In: Chemical Science, 2020, vol. 11, n° 27, p. 7086–7091. doi: 10.1039/D0SC02551H
Main files (1)
Article (Published version)
Identifiers
ISSN of the journal2041-6520
301views
119downloads

Technical informations

Creation07/15/2020 5:58:00 PM
First validation07/15/2020 5:58:00 PM
Update time03/15/2023 10:17:43 PM
Status update03/15/2023 10:17:42 PM
Last indexation02/12/2024 11:52:53 AM
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack