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Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C[double bond, length as m-dash]O bond cleavage.

ABSTRACT: Organic isocyanates are readily converted to methyl amine products through their hydroboration with HBpin in the presence of a ?-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.

SUBMITTER: Yang Y 

PROVIDER: S-EPMC6092714 | biostudies-literature | 2017 May

REPOSITORIES: biostudies-literature

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Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C[double bond, length as m-dash]O bond cleavage.

Yang Yan Y   Anker Mathew D MD   Fang Jian J   Mahon Mary F MF   Maron Laurent L   Weetman Catherine C   Hill Michael S MS  

Chemical science 20170301 5

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 <i>N</i>-,<i>O</i>-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 borylo  ...[more]

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