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
References and Notes
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Typical Procedure
for the N-Arylation of Bis(
ortho
-substituted aryl)amines 2
1 or 4 (1.5 mmol) was added to a mixture of
(t -Bu)3 P (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 H2 O,
and then extracted with EtOAc. The combined organic layer was washed
with brine, dried over Na2 SO4 , and then evaporated
under reduced pressure. The residue was purified with a flash column
chromatography (EtOAc-hexane) to give the desired triarylamine 3 .
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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
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