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Synlett 2010(12): 1819-1824  
DOI: 10.1055/s-0030-1258125
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium-Catalyzed N-Arylation of Bis(ortho-substituted aryl)amines: an Efficient Method for Preparing Sterically Congested Triarylamines

Ryoichi Kuwano*a, Yasuhiro Matsumotoa, Takenori Shigea, Takeshi Tanakaa, Shinichi Sogab, Yasuaki Hanasakib
a Department of Chemistry, Graduate School of Sciences, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
Fax: +81(92)6422572; e-Mail: rkuwano@chem.kyushu-univ.jp;
b Tosoh Organic Chemical Co., Ltd., 4988 Kaisei-cho, Shunan, Yamaguchi 746-0006, Japan
Further Information

Publication History

Received 15 May 2010
Publication Date:
30 June 2010 (online)

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Abstract

Bis(ortho-substituted aryl)amines were arylated on the nitrogen atom with various haloarenes in high yields using the palladium catalyst, which was generated from palladium(II) acetate and tri(tert-butyl)phosphine.

Key words

amination - arylation - cross-coupling - homogeneous catalysis - palladium

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17

Typical Procedure for the N-Arylation of Bis( ortho -substituted aryl)amines 2
Under a nitrogen atmosphere, a haloarene 1 or 4 (1.5 mmol) was added to a mixture of (t-Bu)3P (4.1 mg, 20 µmol), Pd(OAc)2 (2.2 mg, 10 µmol), NaOt-Bu (144 mg, 1.5 mmol), and a diarylamine 2 (1.0 mmol) in toluene (2.0 mL). The reaction mixture was stirred at 120 ˚C for 2-24 h, cooled to r.t., diluted with H2O, and then extracted with EtOAc. The combined organic layer was washed with brine, dried over Na2SO4, and then evaporated under reduced pressure. The residue was purified with a flash column chromatography (EtOAc-hexane) to give the desired triarylamine 3.

22

The competitive experiment using an equimolar mixture of 1g and 1i afforded 3g and 3i by a ratio of 48:52. See details in the Supporting Information.

23

The competitive experiment using an equimolar mixture of 2a and 2c afforded 3a and 3k by a ratio of 32:68. See details in the Supporting Information.