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DOI: 10.1055/s-2005-923596
One-Pot Synthesis of Symmetrical Di- and Triarylamines Using Urea as the Source of the Amino Group
Publication History
Publication Date:
23 December 2005 (online)
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Abstract
A simple one-pot palladium-catalyzed reaction for the conversion of aryl halides to aryl amines using urea as an ammonia equivalent is reported. Arylation of urea in the presence of Pd2dba3, t-Bu3P·HBF4 and t-BuOK in dioxane gives di- and triarylamines in 65-95% yields.
Key words
palladium - arylations - amines - ammonia equivalents - urea
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1a
Hartwig JF. Synlett 1997, 329 -
1b
Hartwig JF. Angew. Chem. Int. Ed. 1998, 37: 2046 -
1c
Wolfe JP.Wagaw S.Marcoux J.-F.Buchwald SL. Acc. Chem. Res. 1998, 31: 805 -
1d
Yang B.Buchwald SL. J. Organomet. Chem. 1999, 576: 125 -
1e
Belfield AJ.Brown GR.Foubister AJ. Tetrahedron 1999, 55: 11399 -
1f
Hartwig JF. Pure Appl. Chem. 1999, 71: 1417 -
1g
Muci AR.Buchwald SL. Top. Curr. Chem. 2002, 219: 131 -
1h
Prim D.Campagne J.Joseph D.Andrioletti B. Tetrahedron 2002, 58: 2041 -
1i
Hartwig JF. In Handbook of Organopalladium Chemistry for Organic Synthesis Vol. 2:Negishi E. Wiley-Interscience; New York: 2002. p.1051 - 2
Huang X.Buchwald SL. Org. Lett. 2001, 3: 3417 -
3a
Artamkina GA.Sergeev AG.Beletskaya IP. Tetrahedron Lett. 2001, 42: 4381 -
3b
Artamkina GA.Sergeev AG.Beletskaya IP. Zh. Org. Khim. 2002, 38: 563 -
4a
Sergeev AG.Artamkina GA.Beletskaya IP. Tetrahedron Lett. 2003, 44: 4719 -
4b
Sergeev AG.Artamkina GA.Beletskaya IP. Zh. Org. Khim. 2003, 39: 1814 -
5a
Wolfe JP.Buchwald SL. Angew. Chem. Int. Ed. 1999, 38: 2413 -
5b
Wolfe JP.Tomori H.Sadighi JP.Yin J.Buchwald SL. J. Org. Chem. 2000, 65: 1158 -
6a
Hartwig JF.Kawatsura M.Hauck SI.Shaughnessy KH.Alcazar-Roman LM. J. Org. Chem. 1999, 64: 5575 -
6b
Stauffer SR.Hartwig JF. J. Am. Chem. Soc. 2003, 125: 6977 -
6c
Stambuli JP.Kuwano R.Hartwig JF. Angew. Chem. Int. Ed. 2002, 41: 4746 -
6d
Strieter ER.Blackmond DG.Buchwald SL. J. Am. Chem. Soc. 2003, 125: 13978 - 8
Netherton MR.Fu GC. Org. Lett. 2001, 3: 4295 - 9
Harris MC.Buchwald SL. J. Org. Chem. 2000, 65: 5327 - 10
Sachinvala N.Winsor DL.Maskos K.Hamed GO.Vigo TL.Bertoniere NR. J. Org. Chem. 2000, 65: 9234
References and Notes
Representative Procedure for Tri(
m
-tolyl)amine.
m-Bromotoluene (282 mg, 1.65 mmol), urea (31 mg, 0.51 mmol), Pd2dba3·CHCl3 (31.5 mg, 0.03 mmol), t-Bu3P·HBF4 (25.2 mg, 0.087 mmol), t-BuOK (325 mg, 2.9 mmol), and anhydrous dioxane (6 mL) purged with argon were placed into an argon-filled reactor. The reaction was carried out with stirring at 100 °C under positive argon pressure. After the aryl halide was completely consumed (according to GC), the reaction mixture was cooled to r.t., diluted with EtOAc (30 mL), filtered through the short plug of Celite® and evaporated on silica gel. The residue was chromatographed on silica gel (Merck 60, 40-63 µm), eluting with light PE, then EtOAc-light PE mixture 1:40 and 1:20 at the end to give 122 mg (85%) of the product as a white solid. Mp 66 °C (ref. 2: 64-65 °C). 1H NMR (400 MHz, acetone-d
6): δ = 7.14 (t, 3 H, 7.7 Hz), 6.77-6.87 (m, 9 H), 2.23 (s, 9 H). MS (EI, 70 eV): m/z (%) = 287 (100) [M+], 271 (2) [M - CH3 - H+], 257 (4) [M+ - 2 CH3], 180 (5) [C13H10N+].