1050505-85-5Relevant articles and documents
Metal-Free Borylation of Heteroarenes Using Ambiphilic Aminoboranes: On the Importance of Sterics in Frustrated Lewis Pair C-H Bond Activation
Légaré Lavergne, Julien,Jayaraman, Arumugam,Misal Castro, Luis C.,Rochette, étienne,Fontaine, Frédéric-Georges
, p. 14714 - 14723 (2017)
Two novel frustrated Lewis pair (FLP) aminoboranes, (1-Pip-2-BH2-C6H4)2 (2; Pip = piperidyl) and (1-NEt2-2-BH2-C6H4)2 (3; NEt2 = diethylamino), were synthesized, and their structural features were elucidated both in solution and in the solid state. The reactivity of these species for the borylation of heteroarenes was investigated and compared to previously reported (1-TMP-2-BH2-C6H4)2 (1; TMP = tetramethylpiperidyl) and (1-NMe2-2-BH2-C6H4)2 (4; NMe2 = dimethylamino). It was shown that 2 and 3 are more active catalysts for the borylation of heteroarenes than the bulkier analogue 1. Kinetic studies and density functional theory calculations were performed with 1 and 2 to ascertain the influence of the amino group of this FLP-catalyzed transformation. The C-H activation step was found to be more facile with smaller amines at the expense of a more difficult dissociation of the dimeric species. The bench-stable fluoroborate salts of all catalysts (1F-4F) have been synthesized and tested for the borylation reaction. The new precatalysts 2F and 3F are showing higher reaction rates and yields for multigram-scale syntheses.
Synthesis of novel fused azecine ring systems through application of the tert-amino effect
Dunkel, Petra,Túrós, Gy?rgy,Bényei, Attila,Ludányi, Krisztina,Mátyus, Péter
experimental part, p. 2331 - 2339 (2010/06/12)
Novel fused azecine ring systems were synthesized via the microwave-assisted thermal isomerization of terphenyl or biphenyl-pyridazine compounds possessing a vinyl and a tert-amino group, through application of a new extension of the tert-amino effect. Substrates for the ring closure were prepared from ortho-dihalobenzene or pyridazinone by consecutive Suzuki couplings with ortho-sec-amino- and formylphenylboronic acids, followed by Knoevenagel condensation of the aldehydes obtained.
