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(Tosylimino)phenyl-λ3-iodane as a Reagent for the Synthesis of Methyl Carbamates via Hofmann Rearrangement of Aromatic and Aliphatic Carboxamides

Akira Yoshimura, Matthew W. Luedtke and Viktor V. Zhdankin*

*Department of Chemistry and Biochemistry, University of Minnesota-Duluth, Duluth, Minnesota 55812, United States, Email: vzhdankid.umn.edu

A. Yoshimura, M. W. Luedtke, V. V. Zhdankin, J. Org. Chem., 2012, 77, 2087-2091.

DOI: 10.1021/jo300007c (free Supporting Information)


Abstract

The use of PhINTs as a reagent enables a mild Hofmann rearrangement of aromatic and aliphatic carboxamides. The mild reaction conditions and high selectivity in the reaction of carboxamides with PhINTs allow the isolation of the initially formed labile isocyanates or their subsequent conversion to stable carbamates by treatment with alcohols.


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proposed mechanism



Hofmann Rearrangement of Carboxamides Mediated by Hypervalent Iodine Species Generated in Situ from Iodobenzene and Oxone: Reaction Scope and Limitations

A. A. Zagulyaeva, C. T. Banek, M. S. Yusubov, V. V. Zhdankin, Org. Lett., 2010, 12, 4644-4647.


Key Words

Hofmann Rearrangement, Hypervalent Iodine Compounds, Carbamates


ID: J42-Y2012-0500