158666-42-3Relevant academic research and scientific papers
A convenient synthesis of 6,6′-dimethyl-2,2′-bipyridine-4-ester and its application to the preparation of bifunctional lanthanide chelators
Havas, Fabien,Danel, Mathieu,Galaup, Chantal,Tisnès, Pierre,Picard, Claude
, p. 999 - 1002 (2007)
We describe a convenient scalable synthesis of 4-carbomethoxy-6,6′-dimethyl-2,2′-bipyridine based on the application of modified Negishi cross-coupling conditions. The use of this building block in the preparation of a number of dissymmetrically 6,6′-tris
Magnetic Anisotropy in Functionalized Bipyridyl Cryptates
Kreidt, Elisabeth,Bischof, Caroline,Platas-Iglesias, Carlos,Seitz, Michael
, p. 5549 - 5557 (2016)
The magnetic properties of molecular lanthanoid complexes are very important for a variety of scientific and technological applications, with the unique magnetic anisotropy being one of the most important features. In this context, a very rigid tris(bipyridine) cryptand was synthesized with a primary amine functionality for future bioconjugation. The magnetic anisotropy was investigated for the corresponding paramagnetic ytterbium cryptate. With the use of a combination of density functional theory calculations and lanthanoid-induced NMR shift analysis, the magnetic susceptibility tensor was determined and compared to the unfunctionalized cryptate analogue. The size and orientation of the axial and rhombic tensor components show remarkably great resilience toward the decrease of local symmetry around the metal and anion exchange in the inner coordination sphere. In addition, the functionalized ytterbium cryptate also exhibits efficient near-IR luminescence.
6,6′-Dimethyl-2,2′-bipyridine-4-ester: A pivotal synthon for building tethered bipyridine ligands
Havas, Fabien,Leygue, Nadine,Danel, Mathieu,Mestre, Béatrice,Galaup, Chantal,Picard, Claude
experimental part, p. 7673 - 7686 (2009/12/06)
We describe an efficient and scalable synthesis of 4-carbomethoxy-6,6′-dimethyl-2,2′-bipyridine starting from easily available substituted 2-halopyridines and based on the application of modified Negishi cross-coupling conditions. This compound is a versatile starting material for the synthesis of 4-functionalized 2,2′-bipyridines bearing halide, alcohol, amine, and other functionalities, suitable for conjugation to biological material (2a-c, 3a-g). The utility of this compound in the construction of more complex architectures was further demonstrated by the synthesis of two bifunctional lanthanide chelators; an open chain ligand based on one 2,2′-bipyridine unit and a cryptand based on three 2,2′-bipyridine units [N2(bpy)3COOMe]. In the field of luminophoric biolabels, the photophysical properties of the corresponding Eu(III) cryptate are reported.
New Symmetric and Unsymmetric Polyfunctionalized 2,2'-Bipyridines
Vains, J. B. Regnouf de,Papet, A. L.,Marsura, A.
, p. 1069 - 1078 (2007/10/02)
Recently, a large number of biheterocycles have been synthesized in order to build macrobicyclic cryptates.To pursue investigations in this field, we prepared new symmetric and unsymmetric functionalized bipyridines and we describe here two synthetic strategies leading to new tetrasubstituted 3 to 15 and trisubstituted 17 to 29 bipyridines.Modification at the α,α'-methyl groups and introduction of functionalities in the 4,4'-positions have been performed after N-O activation of the starting 6,6'-dimethyl-2,2'-bipyridine unit.In the case of cyano and hydroxymethyl groups, alkylation of the N-O function followed by a nucleophilic attack with the CN anion or an hydroxymethyl radical allowed us to obtain the dissymmetric species.To understand observed differencies between cyanation and hydroxymethylation processes, the unstable and hygroscopic N-methoxybipyridinium salt 30 has been isolated and characterized by nmr.Dibromomethyl compounds 8, 15, 29 were finally obtained in good to moderate yields by the Boekelheide rearrangement followed by a pseudohalogen exchange.
