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Synlett 2011(16): 2374-2378  
DOI: 10.1055/s-0030-1260314
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium(II)-Catalyzed Auxiliary-Directed C-H Activation for the Regioselective ortho Arylation of N-(2-Benzoylphenyl)benzamides

Basi V. Subba Reddy*, G. Revathi, A. Srinivas Reddy, Jhillu S. Yadav
Discovery Laboratory, Division of Organic Chemistry, Indian Institute of Chemical Technology, Hyderabad 500007, India
e-Mail: basireddy@iict.res.in;
Further Information

Publication History

Received 3 May 2011
Publication Date:
13 September 2011 (online)

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Abstract

A highly regioselective ortho arylation of N-(2-benzoylphenyl)benzamides has been achieved with aryl iodides in the presence of 10 mol% Pd(OAc)2 and a stoichiometric amount of AgOAc under solvent-free conditions via C-H activation to produce the corresponding 2-arylated benzamides in good yields.

Key words

C-C bond formation - ortho arylation - benzamide - aromatic C-H activation

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General Procedure for the Arylation
A mixture of N-(2-benzoylphenyl)benzamide (1 mmol), AgOAc (1 mmol), Pd(OAc)2 (0.1 mmol), and iodoarene (3 mmol) was heated at 110 ˚C under solvent-free conditions for the appropriate time (see Table  [¹] ) under N2 atmosphere. After completion of the reaction, as indicated by TLC analysis, the reaction mixture was diluted with CH2Cl2 (30 mL) and then filtered under reduced pressure. Removal of the solvent followed by purification on silica gel gave the pure arylated product.
Spectroscopic Data for Selected Products N -(2-Benzoylphenyl)-3,4-dimethoxybiphenyl-2-carboxamide (3h)
IR (neat): 3448, 2931, 2852, 1686, 1638, 1579, 1478, 1442, 1294, 1265, 1160, 1105, 1055, 945, 877, 813, 757, 699, 641 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 10.36 (br s, 1 H), 8.57 (d, J = 8.0 Hz, 1 H), 7.68-6.77 (m, 15 H), 3.93 (s, 3 H), 3.92 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 198.4, 165.9, 151.9, 146.2, 139.3, 139.2, 137.9, 133.5, 132.6, 132.3, 129.9, 128.4, 128.2, 127.9, 127.3, 126.8, 125.5, 124.1, 122.2, 121.9, 113.4, 61.8, 55.9. ESI-MS: m/z = 438 [M + H]. HRMS: m/z calcd for C28H24NO4: 438.1705; found: 438.1686.
N -(2-Benzoylphenyl)-3-nitrobiphenyl-2-carboxamide (3i)
IR (neat): 3454, 1684, 1638, 1584, 1444, 1263 758, 698 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 10.42 (br s, 1 H), 8.44 (d, J = 8.3 Hz, 1 H), 8.12 (dd, J = 9.0, 1.5 Hz, 1 H), 7.68-7.30 (m, 11 H), 7.09-6.98 (m, 3 H), 6.87 (t, J = 7.5 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 198.3, 164.1, 146.9, 141.5, 138.7, 137.7, 137.3, 135.5, 133.6, 132.5, 131.6, 130.0, 129.7, 128.6, 128.2, 128.1, 128.0, 127.9, 124.3, 123.4, 122.8, 122.4. ESI-MS: m/z = 423 [M + H]. HRMS:
m/z calcd for C26H19N2O4: 423.134; found: 423.133.
N -(2-Benzoylphenyl)-4-methylbiphenyl-2-carboxamide (3m)
IR (neat): 3446, 1677, 1639, 1583, 1514, 1441, 1295, 1260, 1194, 1159, 942, 758, 699, 642 cm-¹.¹H NMR (300 MHz, CDCl3): δ = 10.33 (br s, 1 H), 8.67 (d, J = 8.3 Hz, 1 H), 7.59-7.26 (m, 12 H), 7.06 (t, J = 7.7 Hz, 2 H), 6.92 (t, J = 7.3 Hz, 1 H), 6.82 (t, J = 7.3 Hz, 1 H), 2.44 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 198.0, 168.8, 139.5, 138.0, 137.3, 136.8, 136.0, 133.6, 132.7, 132.3, 131.1, 130.3, 130.0, 129.1, 128.7, 128.1, 128.0, 127.9, 127.1, 124.0, 122.1, 121.4, 20.9. ESI-MS: m/z = 392 [M + H]. HRMS: m/z calcd for C27H22NO2: 392.1650; found: 392.1669.
N -(2-Benzoylphenyl)-4,4-dimethylbiphenyl-2-carboxamide (3n)
IR (neat): 3520, 2924, 1679, 1639, 1581, 1259, 771, 699 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 10.36 (br s, 1 H), 8.68 (d, J = 8.1 Hz, 1 H), 7.61-7.22 (m, 12 H), 7.01 (t, J = 7.7 Hz, 1 H), 6.90 (d, J = 7.5 Hz, 2 H), 2.44 (s, 3 H), 1.97 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 197.9, 169.0, 139.7, 138.0, 137.1, 136.9, 136.8, 136.7, 136.6, 135.9, 133.6, 132.8, 132.3, 131.2, 130.3, 129.9, 129.2, 128.8, 128.6, 128.3, 128.1, 124.0, 122.0, 121.5, 20.9, 20.8. ESI-MS: m/z = 406 [M + H]. HRMS: m/z calcd for C28H24NO2: 406.1807; found: 406.1807.