π-π Catalysis Made Asymmetric—Enantiomerization Catalysis Mediated by the Chiral π-System of a Perylene Bisimide Cyclophane

Manuel Weh, Asja A. Kroeger, Kazutaka Shoyama, Matthias Grüne, Amir Karton, Frank Würthner

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

Enzymes actuate catalysis through a combination of transition state stabilization and ground state destabilization, inducing enantioselectivity through chiral binding sites. Here, we present a supramolecular model system which employs these basic principles to catalyze the enantiomerization of [5]helicene. Catalysis is hereby mediated not through a network of functional groups but through π-π catalysis exerted from the curved aromatic framework of a chiral perylene bisimide (PBI) cyclophane offering a binding pocket that is intricately complementary with the enantiomerization transition structure. Although transition state stabilization originates simply from dispersion and electrostatic interactions, enantiomerization kinetics are accelerated by a factor of ca. 700 at 295 K. Comparison with the meso-congener of the catalytically active cyclophane shows that upon configurational inversion in only one PBI moiety the catalytic effect is lost, highlighting the importance of precise transition structure recognition in supramolecular enzyme mimics.

Original languageEnglish
Article numbere202301301
Number of pages10
JournalAngewandte Chemie - International Edition
Volume62
Issue number19
DOIs
Publication statusPublished - 2 May 2023

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