Anion–π Catalysis Enabled by the Mechanical Bond**
John R. J. Maynard, Bartomeu Galmés, Α. Στέργιου, Mark D. Symes, Antonio Frontera, Stephen M. Goldup
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.
Topics & Concepts
RotaxaneCatalysisSelectivityChemistryDecarboxylationIonElectrochemistryAxleStereochemistryCombinatorial chemistrySupramolecular chemistryMoleculeOrganic chemistryElectrodePhysical chemistryThermodynamicsPhysicsSupramolecular Chemistry and ComplexesMolecular Sensors and Ion DetectionCrystallography and molecular interactions