Anion-π Catalysis Enabled by the Mechanical Bond

John R J Maynard; Bartomeu Galmés; Athanasios D Stergiou; Mark D Symes; Antonio Frontera; Stephen M Goldup

doi:10.1002/anie.202115961

Anion-π Catalysis Enabled by the Mechanical Bond

Angew Chem Int Ed Engl. 2022 Mar 14;61(12):e202115961. doi: 10.1002/anie.202115961. Epub 2022 Feb 3.

Authors

John R J Maynard¹, Bartomeu Galmés², Athanasios D Stergiou³, Mark D Symes³, Antonio Frontera², Stephen M Goldup¹

Affiliations

¹ Chemistry, University of Southampton, Highfield, Southampton, S017 1BJ, UK.
² Department of Chemistry, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122, Palma de Mallorca, Baleares, Spain.
³ WestCHEM School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow, G12 8QQ, UK.

Abstract

We report a series of rotaxane-based anion-π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.

Keywords: Anion-π Catalysis; DFT Calculations; Mechanical Bonds; Rotaxanes; Supramolecular Chemistry.

Abstract

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