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

doi:10.1055/s-0030-1260314

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Synlett 2011(16): 2374-2378
DOI: 10.1055/s-0030-1260314

LETTER

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;

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Publikationsverlauf

Received 3 May 2011
Publikationsdatum:
13. September 2011 (online)

Abstract
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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

References and Notes

1a Beccalli EM. Broggini G. Martinelli M. Sottocornola S. Chem. Rev. 2007, 107: 5318

Suche in Google Scholar
1b Alberico D. Scott ME. Lautens M. Chem. Rev. 2007, 107: 174

Suche in Google Scholar
1c Lane BS. Brown MA. Sames D. J. Am. Chem. Soc. 2005, 127: 8050

Suche in Google Scholar
1d Wen J. Zhang J. Chen S.-Y. Li J. Yu X.-Q. Angew. Chem. Int. Ed. 2008, 47: 8897

Suche in Google Scholar
2a Lyons TW. Sanford MS. Chem. Rev. 2010, 110: 1147

Suche in Google Scholar
2b Daugulis O. Do H.-Q. Shabashov D. Acc. Chem. Res. 2009, 42: 1074

Suche in Google Scholar
2c Chen X. Hao X.-S. Goodhue CE. Yu J.-Q. J. Am. Chem. Soc. 2006, 128: 6790

Suche in Google Scholar
2d Inamoto K. Saito T. Katsuno M. Sakamoto T. Hiroya K. Org. Lett. 2007, 9: 2931

Suche in Google Scholar
2e Giri R. Chen X. Yu J.-Q. Angew. Chem. Int. Ed. 2005, 44: 2112

Suche in Google Scholar
3a Desai LV. Ren DT. Rosner T. Org. Lett. 2010, 12: 1032

Suche in Google Scholar
3b Desai LV. Stowers KJ. Sanford MS. J. Am. Chem. Soc. 2008, 130: 13285

Suche in Google Scholar
3c Chernyak N. Dudnik AS. Huang C. Gevorgyan V. J. Am. Chem. Soc. 2010, 132: 8270

Suche in Google Scholar
3d Yoshikai N. Matsumoto A. Norinder J. Nakamura E. Angew. Chem. Int. Ed. 2009, 48: 2925

Suche in Google Scholar
3e Zhao X. Yeung CS. Dong VM. J. Am. Chem. Soc. 2010, 132: 5837

Suche in Google Scholar
3f Gu S. Chen C. Chen W. J. Org. Chem. 2009, 74: 7203

Suche in Google Scholar
4a Yu J.-Q. Giri R. Chen X. Org. Biomol. Chem. 2006, 4: 4041

Suche in Google Scholar
4b Shabashov D. Daugulis O. Org. Lett. 2005, 7: 3657

Suche in Google Scholar
4c Dick AR. Sanford MS. Tetrahedron 2006, 62: 2439

Suche in Google Scholar
4d Daugulis O. Zaitsev VG. Shabashov D. Pham Q.-N. Lazareva A. Synlett 2006, 3382
4e Chen X. Engle KM. Wang D.-H. Yu J.-Q. Angew. Chem. Int. Ed. 2009, 48: 5094

Suche in Google Scholar
4f Wasa M. Worrell BT. Yu J.-Q. Angew. Chem. Int. Ed. 2010, 49: 1275

Suche in Google Scholar
5a Kakiuchi F. Kan S. Igi K. Chatani N. Murai S.
J. Am. Chem. Soc. 2003, 125: 1698

Suche in Google Scholar
5b Bedford RB. Coles SJ. Hursthouse MB. Limmert ME. Angew. Chem. Int. Ed. 2003, 42: 112

Suche in Google Scholar
5c Caron L. Campeau L.-C. Fagnou K. Org. Lett. 2008, 10: 4533

Suche in Google Scholar
5d Cho SH. Hwang SJ. Chang S. J. Am. Chem. Soc. 2008, 130: 9254

Suche in Google Scholar
5e Chen X. Li J.-J. Hao X.-S. Goodhue CE. Yu J.-Q. J. Am. Chem. Soc. 2006, 128: 78

Suche in Google Scholar
5f Chiong HA. Pham Q.-N. Daugulis O. J. Am. Chem. Soc. 2007, 129: 9879

Suche in Google Scholar
5g Desai LV. Stowers KJ. Sanford MS. J. Am. Chem. Soc. 2008, 130: 13285

Suche in Google Scholar
5h Shi Z. Li B. Wan X. Cheng J. Fang Z. Cao B. Qin C. Wang Y. Angew. Chem. Int. Ed. 2007, 46: 5554

Suche in Google Scholar
6a Phipps RJ. Gaunt MJ. Science 2009, 323: 1593

Suche in Google Scholar
6b Zhang Y.-H. Shi B.-F. Yu J.-Q. J. Am. Chem. Soc. 2009, 131: 5072

Suche in Google Scholar
7a Lazareva A. Daugulis O. Org. Lett. 2006, 8: 5211

Suche in Google Scholar
7b Shabashov D. Daugulis O. Org. Lett. 2006, 8: 4947

Suche in Google Scholar
7c Wang D.-H. Wasa M. Giri R. Yu J.-Q. J. Am. Chem. Soc. 2008, 130: 7190

Suche in Google Scholar
8a Zaitsev VG. Shabashov D. Daugulis O. J. Am. Chem. Soc. 2005, 127: 13154

Suche in Google Scholar
8b Reddy BVS. Reddy LR. Corey EJ. Org. Lett. 2006, 8: 3391

Suche in Google Scholar
8c Do H.-Q. Daugulis O. J. Am. Chem. Soc. 2008, 130: 1128

Suche in Google Scholar
9 Reddy BVS. Ramesh K. Yadav JS. Synlett 2011, 169

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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.