Palladium/Proazaphosphatrane-Catalyzed Amination of Aryl Halides
FULL PAPERS
(75 MHz, CDCl3): d¼169.0, 149.3, 145.8, 132.5, 129.4, 122.2,
121.9, 120.8, 119.4, 40.6, 24.5.
& Sons, Chichester, 1999, p. 221; b) T. L. Rathman,
Chem. Spec. 1989, 9, 300; c) M. W. Rathke, J. Am.
Chem. Soc. 1970, 92, 3222.
N-[4’-(4-Methylphenyl)-amino]-acetanilide[6] (Table 2, en-
1
try 20): H NMR (300 MHz, CDCl3): d¼7.86 (bs, 1H), 7.36
[2] J. Louie, J. F. Hartwig, Tetrahedron Lett. 1995, 36, 3609.
[3] J. Br¸ning, Tetrahedron Lett. 1997, 38, 3187.
[4] S. Lee, M. J˘rgensen, J. F. Hartwig, Org. Lett. 2001, 3,
2729.
[5] X. Huang, S. L. Buchwald, Org. Lett. 2001, 3, 3417.
[6] M. C. Harris, X. Huang, S. L. Buchwald, Org. Lett. 2002,
4, 2885.
[7] X. Huang, K. W. Anderson, D. Zim, L. Jiang, A. Klapars,
S. L. Buchwald, J. Am. Chem. Soc. 2003, 125, 6653.
[8] S. Urgaonkar, M. Nagarajan, J. G. Verkade, Tetrahedron
Lett. 2002, 43, 8921.
[9] a) S. Urgaonkar, M. Nagarajan, J. G. Verkade, J. Org.
Chem. 2003, 68, 452; b) S. Urgaonkar, M. Nagarajan,
J. G. Verkade, Org. Lett. 2003, 5, 815.
[10] a) J. You, J. G. Verkade, J. Org. Chem. 2003, 68, 8003;
b) J. You, J. G. Verkade, Angew. Chem. Int. Ed. 2003,
42, 5051.
[11] For recent reviews, see: a) J. G. Verkade, Top. Curr.
Chem. 2002, 233, 1; b) P. B. Kisanga, J. G. Verkade, Tetra-
hedron 2003, 59, 7819; c) J. G. Verkade, P. B. Kisanga, Al-
drichima Acta 2004, 37, 3.
[12] For reviews, see: a) A. R. Muci, S. L. Buchwald, Top.
Curr. Chem. 2002, 219, 131; b) J. F. Hartwig, in: Modern
Amination Methods, (Ed.: A. Ricci) Wiley-VCH, Wein-
heim, 2000; c) B. H. Yang, S. L. Buchwald, J. Organomet.
Chem. 1999, 576, 125; d) J. P. Wolfe, S. Wagaw, J. -F. Mar-
coux, S. L. Buchwald, Acc. Chem. Res. 1998, 31, 805;
e) J. F. Hartwig, Acc. Chem. Res. 1998, 31, 805; f) J. F.
Hartwig, Angew. Chem. Int. Ed. 1998, 37, 2046.
[13] The reaction in THF alone as the solvent also furnished
the desired product but in only moderate yields com-
pared with the toluene-THF solvent system.
[14] Similar speculations were also made by Buchwald, see
Ref.[6]
7.33 (m, 2H), 7.07 7.04 (m, 2H), 6.95 6.91 (m, 4H), 5.65 (bs,
1H), 2.29 (s, 3H), 2.12 (s, 3H); 13C NMR (75 MHz, CDCl3):
d¼169.0, 141.0, 140.7, 131.2, 130.7, 130.1, 122.2, 118.4, 118.0,
24.5, 20.9.
4’-(N-Phenyl-N’-methylamino)-acetophenone[25] (Table 2,
entry 21): 1H NMR (300 MHz, CDCl3): d¼7.83 7.80 (m,
2H), 7.44 7.38 (m, 2H), 7.26 7.20 (m, 3H), 6.77 6.74 (m,
2H), 3.37 (s, 3H), 2.51 (s, 3H); 13C NMR (75 MHz, CDCl3):
d¼196.6, 152.9, 147.5, 130.4, 130.1, 127.3, 126.4, 125.9, 113.6,
40.5, 26.4.
3’-(Morpholin-4-yl-)-acetophenone[26] (Table 2, entry 22):
1H NMR (300 MHz, CDCl3): d¼7.49 7.31 (m, 3H), 7.11
7.07 (m, 1H), 3.86 3.82 (m, 4H), 3.20 3.16 (m, 4H), 2.56 (s,
3H); 13C NMR (75 MHz, CDCl3): d¼198.6, 151.7, 138.2,
129.5, 120.5, 114.6, 67.0, 49.3, 27.0.
3’-(Piperidin-4-yl-)-acetophenone[27] (Table 2, entry 23):
1H NMR (300 MHz, CDCl3): d¼7.51 7.50 (m, 1H), 7.38
7.28 (m, 2H), 7.14 7.10 (m, 1H), 3.22 3.18 (m, 4H), 2.57 (s,
3H), 1.74 1.67 (m, 4H), 1.62 1.54 (m, 2H); 13C NMR
(75 MHz, CDCl3): d¼198.9, 152.5, 138.1, 129.3, 121.3, 119.5,
115.4, 67.0, 50.6, 27.0, 25.9, 24.4.
3’-(N-Phenyl-N’-methylamino)-acetophenone[6] (Table 2,
entry 24): 1H NMR (300 MHz, CDCl3): d¼7.56 7.55 (m,
1H), 7.48 7.44 (m, 1H), 7.35 7.27 (m, 3H), 7.15 7.03 (m,
4H), 3.36 (s, 3H), 2.56 (s, 3H); 13C NMR (100 MHz, CDCl3):
d¼198.6, 149.6, 148.7, 138.5, 129.8, 129.4, 123.5, 122.7, 120.6,
117.6, 40.6, 27.0.
4-(N-Phenyl-N’-methylamino)-benzamide[28] (Table 2, en-
1
try 25): H NMR (300 MHz, CDCl3): d¼7.68 7.65 (m, 2H),
7.41 7.35 (m, 2H), 7.20 7.18 (m, 3H), 6.81 6.78 (m, 2H),
6.04 (bs, 2H), 3.35 (s, 3H); 13C NMR (75 MHz, CDCl3): d¼
169.6, 152.1, 147.8, 130.0, 129.0, 125.7, 125.3, 122.6, 114.6, 40.4.
N-(4’-Piperidin-4-ylphenyl)-acetanilide[29] (Table 2, entry
1
31): H NMR (300 MHz, CDCl3): d¼7.62 (bs, 1H), 7.35 (d,
J¼8.9 Hz, 2H), 6.87 (d, J¼8.9 Hz, 2H), 3.09 3.06 (m, 4H),
2.10 (s, 3H), 1.72 1.65 (m, 4H), 1.58 1.52 (m, 2H); 13C NMR
(75 MHz, CDCl3): d¼168.7, 149.6, 130.2, 121.8, 117.2, 51.3,
26.1, 24.5, 24.4.
[15] B. L. Lucht, D. B. Collum, Acc. Chem. Res. 1999, 32, 1035
and references cited therein.
[16] Ligand 1 is available from Aldrich and Strem Chemicals.
[17] P. B. Kisanga, J. G. Verkade, Tetrahedron 2001, 57, 467.
[18] L. Shi, M. Wang, C. Fan, F. Zhang, Y. Tu, Org. Lett. 2003,
5, 3515.
N-tert-Butoxycarbonyl-4-(4-hydroxyphenyl)-piperazine[30]
(Table 2, entry 33): 1H NMR (300 MHz, CDCl3): d¼6.84 6.75
(m, 5H), 3.58 3.55 (m, 4H), 2.98 2.94 (m, 4H), 1.48 (m, 9H);
13C NMR (75 MHz, CDCl3): d¼155.2, 151.2, 145.2, 119.5,
116.2, 80.5, 51.4, 28.7.
[19] S. Kimura, T. Kobayashi, S. Ishige, Ger. Offen. 2,049,527,
1971; Chem. Abstr. 1971, 75, 22500.
[20] M. Skowronska-Ptasainska, W. Verboom, D. N. Rein-
houdt, J. Org. Chem. 1985, 50, 2690.
[21] K. L. Holland, T. A. Morris, P. J. Nava, M. Zabic, Tetra-
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[22] M. S. Egbertson, L. M. Turchi, G. D. Hartman, W. Halc-
zenko, D. B. Whitman, J. J. Perkins, A. E. Krause, N. Ihle,
D. A. Claremon, PCTInt. Appl. 9412181, 1994; Chem.
Abstr. 1994, 122, 315098.
Acknowledgements
We thank the Aldrich Chemical Company for generously sup-
plying research samples. The National Science Foundation is
gratefully acknowledged for financial support of this work in
the form of a grant.
[23] K. Wedemeyer, S. Boehm, Ger. Offen. 2024859, 1981;
Chem. Abstr. 1981, 95, 6770.
[24] J. B. Christensen, N. Schioedt, K. Bechgaard, T. Buch-
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References and Notes
[1] a) H. J. Reich, J. H. Rigby, in: Handbook of Reagents for
Organic Synthesis, Acidic and Basic Reagents, John Wiley
Adv. Synth. Catal. 2004, 346, 611 616
asc.wiley-vch.de
¹ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
615