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Issue 5, 2017
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Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C<img border='0' src='http://www.rsc.org/images/entities/h2_char_e001.gif' alt='[double bond, length as m-dash]'/>O bond cleavage

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Abstract

Organic isocyanates are readily converted to methyl amine products through their hydroboration with HBpin in the presence of a β-diketiminato magnesium catalyst. Although borylated amide and N-,O-bis(boryl)hemiaminal species have been identified as intermediates during the reductive catalysis, the overall reduction and C–O activation is metal-mediated and proposed to occur through the further intermediacy of well-defined magnesium formamidato, formamidatoborate and magnesium boryloxide derivatives. Examples of all these species have been identified and fully characterised through stoichiometric reactivity studies and the stability of the borate species leads us to suggest that, under catalytic conditions, the onward progress of the deoxygenation reaction is crucially dependent on the further activation provided by the Lewis acidic HBpin substrate. These deductions have been explored and ratified through a DFT study.

Graphical abstract: Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C<img border='0' src='http://www.rsc.org/images/entities/char_e001.gif' alt='[double bond, length as m-dash]'/>O bond cleavage

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Publication details

The article was received on 10 Jan 2017, accepted on 28 Feb 2017 and first published on 01 Mar 2017


Article type: Edge Article
DOI: 10.1039/C7SC00117G
Citation: Chem. Sci., 2017,8, 3529-3537
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    Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C<img border='0' src='http://www.rsc.org/images/entities/h2_char_e001.gif' alt='[double bond, length as m-dash]'/>O bond cleavage

    Y. Yang, M. D. Anker, J. Fang, M. F. Mahon, L. Maron, C. Weetman and M. S. Hill, Chem. Sci., 2017, 8, 3529
    DOI: 10.1039/C7SC00117G

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