Issue 5, 2017

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 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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
10 Jan 2017
Accepted
28 Feb 2017
First published
01 Mar 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 3529-3537

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

Y. Yang, M. D. Anker, J. Fang, M. F. Mahon, L. Maron, C. Weetman and M. S. Hill, Chem. Sci., 2017, 8, 3529 DOI: 10.1039/C7SC00117G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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