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

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.

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

References and Notes

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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.