Hydrodeoxygenation of isocyanates: Snapshots of a magnesium-mediated CO bond cleavage

Yan-Yan Yang, Mathew D. Anker, Jian Fang, Mary F. Mahon, Laurent Maron, Catherine Weetman, Michael S. Hill

Research output: Contribution to journalArticle

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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.

LanguageEnglish
Pages3529-3537
Number of pages9
JournalChemical Science
Volume8
Issue number5
DOIs
StatusPublished - 1 Mar 2017

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Isocyanates
Carbon Monoxide
Magnesium
Chemical activation
Borates
Discrete Fourier transforms
Amides
Catalysis
Amines
Metals
Derivatives
Catalysts
Substrates

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Hydrodeoxygenation of isocyanates : Snapshots of a magnesium-mediated CO bond cleavage. / Yang, Yan-Yan; Anker, Mathew D.; Fang, Jian; Mahon, Mary F.; Maron, Laurent; Weetman, Catherine; Hill, Michael S.

In: Chemical Science, Vol. 8, No. 5, 01.03.2017, p. 3529-3537.

Research output: Contribution to journalArticle

Yang, Y-Y, Anker, MD, Fang, J, Mahon, MF, Maron, L, Weetman, C & Hill, MS 2017, 'Hydrodeoxygenation of isocyanates: Snapshots of a magnesium-mediated CO bond cleavage' Chemical Science, vol. 8, no. 5, pp. 3529-3537. DOI: 10.1039/c7sc00117g
Yang Y-Y, Anker MD, Fang J, Mahon MF, Maron L, Weetman C et al. Hydrodeoxygenation of isocyanates: Snapshots of a magnesium-mediated CO bond cleavage. Chemical Science. 2017 Mar 1;8(5):3529-3537. Available from, DOI: 10.1039/c7sc00117g
Yang, Yan-Yan ; Anker, Mathew D. ; Fang, Jian ; Mahon, Mary F. ; Maron, Laurent ; Weetman, Catherine ; Hill, Michael S./ Hydrodeoxygenation of isocyanates : Snapshots of a magnesium-mediated CO bond cleavage. In: Chemical Science. 2017 ; Vol. 8, No. 5. pp. 3529-3537
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