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Pnictogen-bonding catalysis: brevetoxin-type polyether cyclizations

Galmés, Bartomeu
Frontera, Antonio
Published in Chemical science. 2020, vol. 11, no. 27, p. 7086-7091
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.
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Research group Groupe Matile
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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 https://archive-ouverte.unige.ch/unige:138455

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Deposited on : 2020-07-16

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