Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C=O bond cleavage - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Chemical Science Year : 2017

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

Abstract

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

Dates and versions

hal-01961169 , version 1 (19-12-2018)

Identifiers

Cite

Yan Yang, Mathew D. Anker, Jian Fang, Mary F. Mahon, Laurent Maron, et al.. Hydrodeoxygenation of isocyanates: snapshots of a magnesium-mediated C=O bond cleavage. Chemical Science, 2017, 8 (5), pp.3529-3537. ⟨10.1039/c7sc00117g⟩. ⟨hal-01961169⟩
25 View
0 Download

Altmetric

Share

Gmail Mastodon Facebook X LinkedIn More