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

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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

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Publication details

The article was received on 15 Feb 2018, accepted on 26 Mar 2018 and first published on 09 Apr 2018


Article type: Edge Article
DOI: 10.1039/C8SC00775F
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY-NC license
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    Iron-catalyzed urea synthesis: dehydrogenative coupling of methanol and amines

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

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