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Open AccessArticle

Chiral Chalcogen Bond Donors Based on the 4,4′-Bipyridine Scaffold

1
Strasbourg Institut of Chemistry, UMR CNRS 7177, Team LASYROC, 1 rue Blaise Pascal, University of Strasbourg, 67008 Strasbourg CEDEX, France
2
Crystallography, Magnetic Resonance and Modelisations (CRM2), UMR CNRS 7036, University of Lorraine, Bd des Aiguillettes, 54506 Vandoeuvre-les-Nancy, France
3
Institute of Biomolecular Chemistry ICB, CNR, Secondary branch of Sassari, Traversa La Crucca 3, Regione Baldinca, 07100 Li Punti, Sassari, Italy
4
Department of Molecular Science and Nanosystems DSMN, Ca’ Foscari University of Venice, Via Torino 155, 30172 Mestre Venice, Italy
*
Authors to whom correspondence should be addressed.
Molecules 2019, 24(24), 4484; https://doi.org/10.3390/molecules24244484
Received: 7 November 2019 / Revised: 29 November 2019 / Accepted: 3 December 2019 / Published: 6 December 2019
(This article belongs to the Special Issue Bipyridines: Synthesis, Functionalization and Applications)
Organocatalysis through chalcogen bonding (ChB) is in its infancy, as its proof-of-principle was only reported in 2016. Herein, we report the design and synthesis of new chiral ChB donors, as well as the catalytic activity evaluation of the 5,5′-dibromo-2,2′-dichloro-3-((perfluorophenyl)selanyl)-4,4′-bipyridine as organocatalyst. The latter is based on the use of two electron-withdrawing groups, a pentafluorophenyl ring and a tetrahalo-4,4′-bipyridine skeleton, as substituents at the selenium center. Atropisomery of the tetrahalo-4,4′-bipyridine motif provides a chiral environment to these new ChB donors. Their synthesis was achieved through either selective lithium exchange and trapping or a site-selective copper-mediated reaction. Pure enantiomers of the 3-selanyl-4,4′-bipyridine were obtained by high performance liquid chromatography enantioseparation on specific chiral stationary phase, and their absolute configuration was assigned by comparison of the measured and calculated electronic circular dichroism spectra. The capability of the selenium compound to participate in σ-hole-based interactions in solution was studied by 19F NMR. Even if no asymmetric induction has been observed so far, the new selenium motif proved to be catalytically active in the reduction of 2-phenylquinoline by Hantzsch ester. View Full-Text
Keywords: atropisomerism; 4,4′-bipyridine; chalcogen bond; electronic circular dichroism; noncovalent interactions; organocatalysis; selenium; σ-hole atropisomerism; 4,4′-bipyridine; chalcogen bond; electronic circular dichroism; noncovalent interactions; organocatalysis; selenium; σ-hole
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MDPI and ACS Style

Weiss, R.; Aubert, E.; Peluso, P.; Cossu, S.; Pale, P.; Mamane, V. Chiral Chalcogen Bond Donors Based on the 4,4′-Bipyridine Scaffold. Molecules 2019, 24, 4484.

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