Convenient Access to Functionalized Non-Symmetrical Atropisomeric 4,4′-Bipyridines

Emmanuel Aubert (1) , Emmanuel Wenger (1) , Paola Peluso (2) , Victor Mamane (3)

1 CRM2 - Cristallographie, Résonance Magnétique et Modélisations
2 ICB - Istituto di chimica biomolecolare [Padova, Italy]
3 Institut de Chimie de Strasbourg

Non-symmetrical chiral 4,4′-bipyridines have recently found interest in organocatalysis and medicinal chemistry. In this regard, the development of efficient methods for their synthesis is highly desirable. Herein, a series of non-symmetrical atropisomeric polyhalogenated 4,4′-bipyridines were prepared and further functionalized by using cross-coupling reactions. The desymmetrization step is based on the N-oxidation of one of the two pyridine rings of the 4,4′-bipyridine skeleton. The main advantage of this methodology is the possible post-functionalization of the pyridine N-oxide, allowing selective introduction of chlorine, bromine or cyano groups in 2- and 2′-postions of the chiral atropisomeric 4,4′-bipyridines. The crystal packing in the solid state of some newly prepared derivatives was analyzed and revealed the importance of halogen bonds in intermolecular interactions

Mots clés: 4 4'-bipyridine; pyridine N-oxidation; halogenation; halogen bond; cyanation; Finkelstein reaction; Suzuki coupling

Domaines: Chimie organique

Emmanuel Aubert, Emmanuel Wenger, Paola Peluso, Victor Mamane. Convenient Access to Functionalized Non-Symmetrical Atropisomeric 4,4′-Bipyridines. Compounds, 2021, 1 (2), pp.58 - 74. ⟨10.3390/compounds1020006⟩. ⟨hal-03331281⟩