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J Am Chem Soc. 2016 Sep 28;138(38):12605-14. doi: 10.1021/jacs.6b07486. Epub 2016 Sep 15.

(NHC)Cu-Catalyzed Mild C-H Amidation of (Hetero)arenes with Deprotectable Carbamates: Scope and Mechanistic Studies.

Xie W1,2, Yoon JH1,2, Chang S1,2.

Author information

1
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS) , Daejeon 305-701, South Korea.
2
Department of Chemistry, Korea Advanced Institute of Science & Technology (KAIST) , Daejeon 305-701, South Korea.

Abstract

Primary arylamines are an important unit broadly found in synthetic, biological, and materials science. Herein we describe the development of a (NHC)Cu system that mediates a direct C-H amidation of (hetero)arenes by using N-chlorocarbamates or their sodio derivatives as the practical amino sources. A facile stoichiometric reaction of reactive copper-aryl intermediates with the amidating reagent led us to isolate key copper arylcarbamate species with the formation of a C-N bond. The use of (t)BuONa base made this transformation catalytic under mild conditions. The present (NHC)Cu-catalyzed C-H amidation works efficiently and selectively on a large scale over a range of arenes including polyfluorobenzenes, azoles, and quinoline N-oxides. Deprotection of the newly installed carbamate groups such as Boc and Cbz was readily performed to afford the corresponding primary arylamines.

PMID:
27585065
DOI:
10.1021/jacs.6b07486

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