title: Large-Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties.
abstract: A convenient and efficient gram-scale synthesis for enantiopure hemicryptophane-tren (tren=tris(2-aminoethyl)amine) derivatives has been developed. The four-step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C3symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France.
authors.forename: Sara
authors.initials: S
authors.lastname: Lefevre
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France.
authors.forename: Dawei
authors.initials: D
authors.lastname: Zhang
authors.affiliation: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.|Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France.
authors.forename: Estelle
authors.initials: E
authors.lastname: Godart
authors.affiliation: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors.forename: Marion
authors.initials: M
authors.lastname: Jean
authors.affiliation: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Vanthuyne
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France.
authors.forename: Jean-Christophe
authors.initials: JC
authors.lastname: Mulatier
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France.
authors.forename: Jean-Pierre
authors.initials: JP
authors.lastname: Dutasta
authors.affiliation: Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France.
authors.forename: Laure
authors.initials: L
authors.lastname: Guy
authors.affiliation: Aix Marseille Université, Centrale Marseille, CNRS, iSm2 UMR 7313, 13397, Marseille, France. alexandre.martinez@centrale-marseille.fr.|Laboratoire de Chimie, École Normale Supérieure de Lyon, CNRS, UCBL, 46, Allée d'Italie, 69364, Lyon, France. alexandre.martinez@centrale-marseille.fr.
authors.forename: Alexandre
authors.identifier: http://orcid.org/0000-0002-6745-5734
authors.initials: A
authors.lastname: Martinez
keywords: cage compounds; configuration determination; hemicryptophanes; molecular recognition; supramolecular chemistry