title: Asymmetric Anion-π Catalysis on Perylenediimides.
abstract: Anion-π catalysis, that is the stabilization of anionic transition states on π-acidic aromatic surfaces, has so far been developed with naphthalenediimides (NDIs). This report introduces perylenediimides (PDIs) to anion-π catalysis. The quadrupole moment of PDIs (+23.2 B) is found to exceed that of NDIs and reach new records with acceptors in the core (+70.9 B), and their larger surface provides space to better accommodate chemical transformations. Unlike NDIs, the activity of PDI catalysts for enolate and enamine addition is determined by the twist of their π surface rather than their reducibility. These results, further strengthened by nitrate inhibition and circular dichroism spectroscopy, support an understanding of anion-π interactions centered around quadrupole moments, i.e., electrostatic contributions, rather than redox potentials and charge transfer. The large PDI surfaces provide access to the highest enantioselectivities observed so far in anion-π catalysis (96 % ee).
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Chao
authors.initials: C
authors.lastname: Wang
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: François N
authors.initials: FN
authors.lastname: Miros
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Jiri
authors.initials: J
authors.lastname: Mareda
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
authors.forename: Naomi
authors.initials: N
authors.lastname: Sakai
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva, Switzerland. stefan.matile@unige.ch.
authors.forename: Stefan
authors.identifier: 0000-0002-8537-8349
authors.initials: S
authors.lastname: Matile
keywords: anion-π interactions; homogeneous catalysis; perylenediimides; quadrupole moments; redox potentials