Publication 320

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  1. Gini, A.; Paraja, M.; Galmés, B.; Besnard, C.; Poblador-Bahamonde, A. I.; Sakai, N.; Frontera, A.; Matile, S. “Pnictogen-Bonding Catalysis:  Brevetoxin-Type Polyether Cyclizations” Chem. Sci. 2020, 11, 7086-7091

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.

DOI: 10.1039/D0SC02551H 

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