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Pd(OAc)2-Catalyzed Aminocarbonylation of Aryl Iodides
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IR (KBr): 1655 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.12–1.80 (m, 6 H), 1.90–2.05 (m,
4 H), 3.45 (m, 1 H), 8.27 (d, J = 8.8 Hz, 2 H), 8.36 (d, J = 8.8 Hz, 2
1H NMR (400 MHz, CDCl3): d = 3.86 (s, 3 H), 6.94 (d, J = 8.8 Hz,
2 H), 7.10 (t, J = 7.0 Hz, 1 H), 7.33 (t, J = 7.6 Hz, 2 H), 7.71 (d,
J = 7.6 Hz, 2 H), 7.92 (d, J = 8.5 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 165.6, 162.3, 139.5, 138.6, 129.3,
128.8, 127.4, 124.0, 122.2, 120.5, 118.8, 118.7, 113.6, 55.4.
H).
13C NMR (100 MHz, CDCl3): d = 164.7, 149.6, 140.9, 128.5, 128.2,
124.5, 123.9, 49.4, 34.0, 33.2, 29.8, 25.6, 25.0.
GC-MS (EI, 70 eV): m/z (%) = 248 ([M+], 20), 167 (100), 150 (70).
GC–MS (EI, 70 eV): m/z (%) = 227 ([M+], 25), 135 (100).
Acknowledgment
4-Nitro-N-[(3-trifluoromethyl)phenyl]benzamide (Table 2,
Entry 8)
Yellow solid; yield: 62%; mp 192–193 °C.
IR (KBr): 1659 cm–1.
The financial assistance from Technical Education Quality
Improvement Programme (TEQIP), Government of India is kindly
acknowledged.
1H NMR (400 MHz, CDCl3): d = 7.38–7.51 (m, 3 H), 8.1 (s, 1 H),
8.21 (d, J = 8.2 Hz, 2 H), 8.31 (d, J = 8.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d = 164.3, 149.6, 140.4, 139.1, 131.1,
130.8, 129.3, 129.1, 124.3, 123.9, 123.4, 120.9, 117.7, 117.5.
References
(1) (a) Valentine, D. Jr.; Tilley, J. W.; LeMahieu, R. A. J. Org.
Chem. 1981, 46, 4614. (b) Cassar, L.; Foa, M.; Gardano, A.
J. Organomet. Chem. 1976, 121, 55. (c) Grushin, V. V.;
Alper, H. J. Chem. Soc., Chem. Commun. 1992, 611.
(d) Beletskaya, I. P.; Lapidus, A. L.; Petrovskii, K. B. Russ.
J. Org. Chem. 1998, 34, 1464. (e) Lin, Y. S.; Yamamoto, A.
J. Organomet. Chem. 2002, 645, 152.
MS–MS (ESI–): m/z calcd for (M – 1): 309.06; found (M – 1):
309.13.
N-[(3-Trifluoromethyl)phenyl]thiophene-2-carboxamide
(Table 2, Entry 9)
(2) (a) Schoenberg, A.; Heck, R. F. J. Org. Chem. 1974, 39,
3327. (b) Perry, R. J.; Wilson, B. D. Organometallics 1994,
13, 3346. (c) Takahashi, T.; Inoue, H.; Tomida, S.; Doi, T.;
Bray, A. M. Tetrahedron Lett. 1999, 40, 7843.
White solid; yield: 86%; mp 144–145 °C.
IR (KBr): 1640 cm–1.
1H NMR (400 MHz, CDCl3): d = 7.13 (t, J = 4.3 Hz, 1 H), 7.38–
7.58 (m, 3 H), 7.66 (d, J = 3.6 Hz, 1 H), 7.83 (d, J = 7.6 Hz, 1 H),
7.90 (s, 1 H).
13C NMR (100 MHz, CDCl3): d = 160.2, 141.8, 138.8, 138.3, 131.4,
129.8, 129.0, 128.1, 123.4, 121.3, 117.2, 117.1.
GC–MS (EI, 70 eV): m/z (%) = 271 ([M+], 30), 111 (100).
(d) Magerlein, W.; Indolese, A. F.; Beller, M. J. Organomet.
Chem. 2002, 641, 30.
(3) (a) Schoenberg, A.; Bartoletti, I.; Heck, R. F. J. Org. Chem.
1974, 39, 3318. (b) Ben-David, Y.; Portnoy, M.; Milstein,
D. J. Am. Chem. Soc. 1989, 111, 8742. (c) Yang, J.;
Haynes, A.; Maitlis, P. M. Chem. Commun. 1999, 179.
(d) Calo, V.; Giannoccaro, P.; Nacci, A.; Monopoli, A.
Tetrahedron Lett. 2001, 42, 3299. (e) Magerlein, W.;
Beller, M.; Indolese, A. F. J. Mol. Catal. A: Chem. 2000,
156, 213.
N-(2-Fluorophenyl)-1-naphthamide (Table 2, Entry 10)
White solid; yield: 84%; mp 137–138 °C.
IR (KBr): 1653 cm–1.
(4) (a) Ben-David, Y.; Portnoy, M.; Milstein, D. J. Chem. Soc.,
Chem. Commun. 1989, 1816. (b) Okano, T.; Harada, N.;
Kiji, J. Bull. Chem. Soc. Jpn. 1994, 67, 2329.
(5) Stille, J. K. Pure Appl. Chem. 1985, 57, 1771.
(6) (a) Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V.
Carbonylation Direct Synthesis of Carbonyl Compounds;
Plenum Press: New York, 1991. (b) Tsuji, J. Palladium
Reagents and Catalysis; Wiley: Chichester, 1995. (c) Heck,
R. F. Palladium Reagents in Organic Synthesis; Academic
Press: New York, 1985.
1H NMR (400 MHz, CDCl3): d = 7.1–7.6 (m, 7 H), 7.77 (d, J = 7.0
Hz, 1 H), 7.91 (d, J = 7.3 Hz, 1 H), 7.99 (d, J = 8.2 Hz, 1 H), 8.40
(d, J = 7.9 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 167.6, 151.7, 134.2, 134.0, 131.6,
130.3, 128.6, 128.2, 127.7, 126.8, 125.5, 125.4, 124.9, 124.1, 122.1,
115.2, 115.0.
MS–MS (ESI–): m/z calcd for (M – 1): 264.09; found (M – 1):
264.13.
(7) Schoenberg, A.; Heck, R. F. J. Org. Chem. 1974, 39, 3327.
(8) Cai, M.; Huang, Y.; Hu, R.; Song, C. J. Mol. Catal. A: Chem.
2004, 212, 151.
N-Cyclohexyl-1-naphthamide (Table 3, Entry 5)
White solid; yield: 79%; mp 156–157 °C.
IR (KBr): 1643 cm–1.
1H NMR (400 MHz, CDCl3): d = 1.25–1.78 (m, 6 H), 1.86–2.13 (m,
4 H), 4.10 (s, 1 H), 7.26–7.53 (m, 3 H), 7.57 (d, J = 7.0 Hz, 1 H),
7.86 (d, J = 7.3 Hz, 1 H), 7.90 (d, J = 8.2 Hz, 1 H), 8.28 (d, J = 7.6
Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 168.8, 135.2, 133.8, 130.4, 130.2,
128.4, 127.1, 126.4, 125.4, 124.8, 124.7, 48.8, 34.0, 33.3, 25.7,
25.6, 25.0.
(9) Cai, M.; Zhao, H.; Huang, Y. J. Mol. Catal. A: Chem. 2005,
238, 41.
(10) Skoda-Foldes, R.; Takacs, E.; Horvath, J.; Tuba, Z.; Kollar,
L. Green Chem. 2003, 5, 643.
(11) Miller, P. M.; Long, N. J.; Mello, A. J.; Vilar, R.; Passchier,
J.; Gee, A. Chem. Commun. 2006, 546.
(12) Martinelli, J. R.; Clark, T. P.; Watson, D. A.; Munday, R. H.;
Buchwald, S. L. Angew. Chem. Int. Ed. 2007, 46, 8460.
(13) Csajági, C.; Borcsek, B.; Niesz, K.; Kovács, I.; Székelyhidi,
Z.; Bajkó, Z.; Ürge, L.; Darvas, F. Org. Lett. 2008, 10, 1589.
(14) (a) Ionic Liquids in Synthesis; Wasserscheid, P.; Welton, T.,
Eds.; Wiley-VCH: Weinheim, 2003. (b) Chemical
Synthesis Using Supercritical Fluids; Jessop, P. G.; Leitner,
W., Eds.; Wiley-VCH: Weinheim, 1999. (c) Organic
Reactions in Water; Lindström, U. M., Ed.; Blackwell:
Oxford, 2007. (d) Tanaka, K. Solvent-Free Organic
Synthesis; Wiley-VCH: Weinheim, 2003.
GC-MS (EI, 70 eV): m/z (%) = 253 ([M+], 50), 177 (60), 155 (100).
N-Cyclohexyl-4-nitrobenzamide (Table 3, Entry 6)
Yellow solid; yield: 76%; mp 160–161 °C.
IR (KBr): 1627 cm–1.
Synthesis 2008, No. 15, 2347–2352 © Thieme Stuttgart · New York