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Issue 5, 2018
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Reactivity of highly Lewis acidic diborane(4) towards pyridine and isocyanide: formation of boraalkene–pyridine complex and ortho-functionalized pyridine derivatives

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Abstract

The reaction of pinB-BMes2 (pin = pinacolato, Mes = 2,4,6-Me3C6H2) with Xyl-NC (Xyl = 2,6-Me2C6H3) and pyridine results in the formation of a pyridine-coordinated boraalkene that exhibits an intense color caused by an intramolecular charge-transfer interaction. In the presence of an excess of pyridine, the ortho C–H bond of pyridine was selectively functionalized to afford a quinoid compound or an isocyanide-coupled product. Based on the concentration effect, the reaction stoichiometry, and previously reported DFT calculations, a reaction mechanism that involves several rearrangement reactions was proposed. Using the present method, substituted pyridines and N-heterocycles afforded the corresponding functionalized derivatives. A subsequent hydrolysis of one of the resulting products furnished an aminomethylated pyridine derivative in two steps from parent pyridine.

Graphical abstract: Reactivity of highly Lewis acidic diborane(4) towards pyridine and isocyanide: formation of boraalkene–pyridine complex and ortho-functionalized pyridine derivatives

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Publication details

The article was received on 03 Nov 2017, accepted on 10 Dec 2017 and first published on 11 Dec 2017


Article type: Edge Article
DOI: 10.1039/C7SC04759B
Citation: Chem. Sci., 2018,9, 1301-1310
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    Reactivity of highly Lewis acidic diborane(4) towards pyridine and isocyanide: formation of boraalkene–pyridine complex and ortho-functionalized pyridine derivatives

    Y. Katsuma, H. Asakawa and M. Yamashita, Chem. Sci., 2018, 9, 1301
    DOI: 10.1039/C7SC04759B

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