COMMUNICATIONS
Selective Monoarylation of Primary Anilines Catalyzed by Pd(dippf)
Table 3. Highly selective synthesis of tertiary amines.[a]
[a]
The residue originating from the aryl halide (Ar3-X) is placed on the right-hand side. Conditions: 1.00 mmol amine,
1.00 mmol Ar1-Br, 2.40 mmol NaO-t-Bu, 0.5 mol% 6, 0.5 mol% dippf, 2 mL toluene, 808C, 20 h. Then 1.10 mmol Ar3-X in
0.5 mL toluene, 1208C, 24 h, isolated yields.
syringe. The reaction mixture was stirred at 808C for 20 h,
followed by addition of a solution of the second aryl halide
(1.10 mmol) in toluene (0.5 mL) via syringe. The tempera-
ture was increased to 1208C and stirring was continued for
another 24 h. The mixture allowed to cool to room tempera-
ture and diluted with dichloromethane (30 mL) and water
(30 mL). The aqueous layer was separated and extracted
with dichloromethane (220 mL). The combined organic
layers were dried over MgSO4, filtered and concentrated
under vacuum (408C, 500 mbar). The crude product was fur-
ther purified by flash chromatography (basic Al2O3, hexane/
ethyl acetate), yielding the corresponding tertiary amine;
yield: 75–96%.
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Acknowledgements
We thank J. Tang for helpful discussion, the Chinese Scholar-
ship Council (fellowship to F.J.), and A. Leidner for technical
assistance.
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Adv. Synth. Catal. 2016, 358, 1589 – 1594
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