Pnictogen-bonding catalysis: brevetoxin-type polyether cyclizations

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 >...

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Published inChemical science (Cambridge) Vol. 11; no. 27; pp. 786 - 791
Main Authors Gini, Andrea, Paraja, Miguel, Galmés, Bartomeu, Besnard, Celine, Poblador-Bahamonde, Amalia I, Sakai, Naomi, Frontera, Antonio, Matile, Stefan
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 21.07.2020
Subjects
Antimony
Bismuth
Catalysis
Crystallography
Donors (electronic)
Germanium
Hydrogen bonding
Lewis acid
Natural products
Oligomers
Stereoselectivity
Tin
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Summary: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 (SbCl 3 ), 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. This study marks chemical space available for pnictogen-bonding catalysis, and demonstrates that reactivity accessible in this space is unique.
Bibliography:For ESI and crystallographic data in CIF or other electronic format see DOI
1999316-1999326
10.1039/d0sc02551h
Electronic supplementary information (ESI) available: Detailed procedures and results for all reported experiments. CCDC
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ISSN:2041-6520
2041-6539
DOI:10.1039/d0sc02551h