Elucidating the Reactivity of Vicinal Dicarbenoids: From Lewis Adduct Formation to B-C Bond Activation.
作者： Hauke Kelch , Stephanie Kachel , Mehmet Ali Celik , Marius Schäfer , Benedikt Wennemann
关键词: Isomerization 、 Carbene 、 Chemistry 、 Adduct 、 Medicinal chemistry 、 Reactivity (chemistry) 、 Triphenylborane 、 Frustrated Lewis pair 、 Lewis acids and bases 、 Nuclear magnetic resonance spectroscopy 、 Photochemistry
摘要: The reactivity of the diaminoacetylene Pip-C≡C-Pip (Pip=piperidyl=NC5 H10 ) towards phenyldichloro- and triphenylborane is presented. In case less Lewis acidic PhBCl2 , first example a double adduct vicinal dicarbenoid reported. For more triphenylborane, coordination to bifunctional carbene leads mild B-C bond activation, resulting in syn-1,2-carboboration. Ensuing cis/trans isomerization yields novel ethylene-bridged frustrated pair (FLP). compounds were characterized using multinuclear NMR spectroscopy, structural analysis, mass spectrometry. Reactivity studies both isomers with N-heterocyclic 1,3-dimethylimidazol-2-ylidene (IMe) aided elucidating proposed pathway. DFT calculations carried out elucidate reaction mechanism. rather low free energy activation consistent observation that proceeds smoothly at room temperature.
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