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Synlett 2011(13): 1859-1862  
DOI: 10.1055/s-0030-1260954
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Mediated Aryl Amination: In Situ Generation of an Active Copper(I) Species

Takashi Komori, Nobuhiro Satoh, Satoshi Yokoshima, Tohru Fukuyama*
Graduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Fax: +81(3)58028694; e-Mail: fukuyama@mol.f.u-tokyo.ac.jp;
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Publication History

Received 18 May 2011
Publication Date:
14 July 2011 (online)

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Abstract

We have developed novel conditions for copper-mediated aryl amination by using a combination of easy-to-handle and inexpensive Cu(OAc)2˙H2O and phenylhydrazine.

Key words

amine - aryl amination - copper - phenylhydrazine - reductant

11

We reported that the aryl amination reaction with Cu(OAc)2 did not proceed in DMF (ref. 8). DMSO might work as a reductant under these conditions.

13

Typical Procedure: A solution of copper(II) acetate monohydrate (0.40 mmol) and amine (4.0 mmol) in DMSO (1 mL) was stirred for 30 min at r.t., whereupon phenylhydrazine (0.20 mmol) was added. After stirring for 30 min, aryl iodide (1.0 mmol) was added to the solution. The reaction mixture was stirred for 30 min, and the solution was warmed to 90 ˚C. After stirring for 23 h at the same temperature, the solution was cooled to r.t. and diluted with EtOAc. The solution was washed with aq ammoniacal sodium chloride (3 ×). The combined aqueous layer was extracted with EtOAc (3 ×). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography to give the corresponding aniline.