title: Exploring the activation modes of a rotaxane-based switchable organocatalyst.
abstract: The reactivity of a rotaxane that acts as an aminocatalyst for the functionalization of carbonyl compounds through HOMO and LUMO activation pathways has been studied. Its catalytic activity is explored for C-C and C-S bond forming reactions through iminium catalysis, in nucleophilic substitutions and additions through enamine intermediates, in Diels-Alder reactions via trienamine catalysis, and in a tandem iminium-ion/enamine reaction. The catalyst can be switched "on" or "off", effectively controlling the rate of all of these chemical transformations, by the in situ change of the position of the macrocycle between two different binding sites on the rotaxane thread.
authors.affiliation: School of Chemistry, University of Manchester , Oxford Road, Manchester, M13 9PL, United Kingdom.
authors.forename: Victor
authors.initials: V
authors.lastname: Blanco
authors.forename: David A
authors.initials: DA
authors.lastname: Leigh
authors.forename: Urszula
authors.initials: U
authors.lastname: Lewandowska
authors.forename: Bartosz
authors.initials: B
authors.lastname: Lewandowski
authors.forename: Vanesa
authors.initials: V
authors.lastname: Marcos
mesh_terms: D002384:Catalysis; D009930:Organic Chemicals / Q000737:chemistry*; D043862:Rotaxanes / Q000737:chemistry*
chemical_list: D009930:Organic Chemicals; D043862:Rotaxanes