Hydrodeoxygenation of isocyanates : snapshots of a magnesium-mediated C=O bond cleavage

Yang, Yan and Anker, Mathew D. and Fang, Jian and Mahon, Mary F. and Maron, Laurent and Weetman, Catherine and Hill, Michael S. (2017) Hydrodeoxygenation of isocyanates : snapshots of a magnesium-mediated C=O bond cleavage. Chemical Science, 8 (5). pp. 3529-3537. ISSN 2041-6539 (https://doi.org/10.1039/C7SC00117G)

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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.

ORCID iDs

Yang, Yan, Anker, Mathew D., Fang, Jian, Mahon, Mary F., Maron, Laurent, Weetman, Catherine ORCID logoORCID: https://orcid.org/0000-0001-5643-9256 and Hill, Michael S.;
  • Item type:Article
    ID code:73694
    Dates:
    Date
    Event
    1 May 2017
    Published
    1 March 2017
    Published Online
    28 February 2017
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:24 Aug 2020 13:24
    Last modified:11 Nov 2024 12:46
    URI:https://strathprints.strath.ac.uk/id/eprint/73694
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