A Straightforward Synthesis of N-Substituted Ureas from Primary Amides

Nathalie Saraiva Rosa; Thomas Glachet; Quentin Ibert; Jean-François Lohier; Xavier Franck; Vincent Reboul

doi:10.1055/s-0040-1707103

Synthesis, Table of Contents

Synthesis 2020; 52(14): 2099-2105
DOI: 10.1055/s-0040-1707103

paper

A Straightforward Synthesis of N-Substituted Ureas from Primary Amides

Nathalie Saraiva Rosa

^aNormandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France Email: vincent.reboul@ensicaen.fr

,

Thomas Glachet

^aNormandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France Email: vincent.reboul@ensicaen.fr

,

Quentin Ibert

^aNormandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France Email: vincent.reboul@ensicaen.fr

,

Jean-François Lohier

^aNormandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France Email: vincent.reboul@ensicaen.fr

,

Xavier Franck

^bNormandie Univ, CNRS, UNIROUEN, INSA Rouen, COBRA, 76000 Rouen, France

,

Vincent Reboul ∗

^aNormandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France Email: vincent.reboul@ensicaen.fr

› Author Affiliations

Abstract

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Abstract

A direct and convenient method for the preparation of N-substituted ureas is achieved by treating primary amides with phenyliodine diacetate (PIDA) in the presence of an ammonia source (NH₃ or ammonium carbamate) in MeOH. The use of 2,2,2-trifluoroethanol (TFE) as the solvent increases the electrophilicity of the hypervalent iodine species and allows the synthesis of electron-poor carboxamides. This transformation involves a nucleophilic addition of ammonia on the isocyanate intermediate generated in situ by a Hofmann rearrangement of the starting amide.

Key words

amides - ureas - hypervalent iodine - Hofmann rearrangement - isocyanates

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References

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