Issue 16, 2018

Iron-catalyzed urea synthesis: dehydrogenative coupling of methanol and amines

Abstract

Substituted ureas have numerous applications but their synthesis typically requires the use of highly toxic starting materials. Herein we describe the first base-metal catalyst for the selective synthesis of symmetric ureas via the dehydrogenative coupling of methanol with primary amines. Using a pincer supported iron catalyst, a range of ureas was generated with isolated yields of up to 80% (corresponding to a catalytic turnover of up to 160) and with H2 as the sole byproduct. Mechanistic studies indicate a stepwise pathway beginning with methanol dehydrogenation to give formaldehyde, which is trapped by amine to afford a formamide. The formamide is then dehydrogenated to produce a transient isocyanate, which reacts with another equivalent of amine to form a urea. These mechanistic insights enabled the development of an iron-catalyzed method for the synthesis of unsymmetric ureas from amides and amines.

Graphical abstract: Iron-catalyzed urea synthesis: dehydrogenative coupling of methanol and amines

Supplementary files

Article information

Article type
Edge Article
Submitted
15 feb 2018
Accepted
26 mar 2018
First published
09 apr 2018
This article is Open Access

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

Chem. Sci., 2018,9, 4003-4008

Iron-catalyzed urea synthesis: dehydrogenative coupling of methanol and amines

Elizabeth M. Lane, N. Hazari and W. H. Bernskoetter, Chem. Sci., 2018, 9, 4003 DOI: 10.1039/C8SC00775F

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