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

20 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)3529-3537
Number of pages9
JournalChemical Science
Volume8
Issue number5
DOIs
Publication statusPublished - 1 Mar 2017

ASJC Scopus subject areas

  • Chemistry(all)

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