Download PDF
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)

   Permissions and Reprints All articles of this category
Preview

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 
    Search in Google Scholar
  • 1b Alberico D. Scott ME. Lautens M. Chem. Rev.  2007,  107:  174 
    Search in Google Scholar
  • 1c Lane BS. Brown MA. Sames D. J. Am. Chem. Soc.  2005,  127:  8050 
    Search in Google Scholar
  • 1d Wen J. Zhang J. Chen S.-Y. Li J. Yu X.-Q. Angew. Chem. Int. Ed.  2008,  47:  8897 
    Search in Google Scholar
  • 2a Lyons TW. Sanford MS. Chem. Rev.  2010,  110:  1147 
    Search in Google Scholar
  • 2b Daugulis O. Do H.-Q. Shabashov D. Acc. Chem. Res.  2009,  42:  1074 
    Search in Google Scholar
  • 2c Chen X. Hao X.-S. Goodhue CE. Yu J.-Q. J. Am. Chem. Soc.  2006,  128:  6790 
    Search in Google Scholar
  • 2d Inamoto K. Saito T. Katsuno M. Sakamoto T. Hiroya K. Org. Lett.  2007,  9:  2931 
    Search in Google Scholar
  • 2e Giri R. Chen X. Yu J.-Q. Angew. Chem. Int. Ed.  2005,  44:  2112 
    Search in Google Scholar
  • 3a Desai LV. Ren DT. Rosner T. Org. Lett.  2010,  12:  1032 
    Search in Google Scholar
  • 3b Desai LV. Stowers KJ. Sanford MS. J. Am. Chem. Soc.  2008,  130:  13285 
    Search in Google Scholar
  • 3c Chernyak N. Dudnik AS. Huang C. Gevorgyan V. J. Am. Chem. Soc.  2010,  132:  8270 
    Search in Google Scholar
  • 3d Yoshikai N. Matsumoto A. Norinder J. Nakamura E. Angew. Chem. Int. Ed.  2009,  48:  2925 
    Search in Google Scholar
  • 3e Zhao X. Yeung CS. Dong VM. J. Am. Chem. Soc.  2010,  132:  5837 
    Search in Google Scholar
  • 3f Gu S. Chen C. Chen W. J. Org. Chem.  2009,  74:  7203 
    Search in Google Scholar
  • 4a Yu J.-Q. Giri R. Chen X. Org. Biomol. Chem.  2006,  4:  4041 
    Search in Google Scholar
  • 4b Shabashov D. Daugulis O. Org. Lett.  2005,  7:  3657 
    Search in Google Scholar
  • 4c Dick AR. Sanford MS. Tetrahedron  2006,  62:  2439 
    Search 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 
    Search in Google Scholar
  • 4f Wasa M. Worrell BT. Yu J.-Q. Angew. Chem. Int. Ed.  2010,  49:  1275 
    Search in Google Scholar
  • 5a Kakiuchi F. Kan S. Igi K. Chatani N. Murai S.
    J. Am. Chem. Soc.  2003,  125:  1698 
    Search in Google Scholar
  • 5b Bedford RB. Coles SJ. Hursthouse MB. Limmert ME. Angew. Chem. Int. Ed.  2003,  42:  112 
    Search in Google Scholar
  • 5c Caron L. Campeau L.-C. Fagnou K. Org. Lett.  2008,  10:  4533 
    Search in Google Scholar
  • 5d Cho SH. Hwang SJ. Chang S. J. Am. Chem. Soc.  2008,  130:  9254 
    Search in Google Scholar
  • 5e Chen X. Li J.-J. Hao X.-S. Goodhue CE. Yu J.-Q. J. Am. Chem. Soc.  2006,  128:  78 
    Search in Google Scholar
  • 5f Chiong HA. Pham Q.-N. Daugulis O. J. Am. Chem. Soc.  2007,  129:  9879 
    Search in Google Scholar
  • 5g Desai LV. Stowers KJ. Sanford MS. J. Am. Chem. Soc.  2008,  130:  13285 
    Search 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 
    Search in Google Scholar
  • 6a Phipps RJ. Gaunt MJ. Science  2009,  323:  1593 
    Search in Google Scholar
  • 6b Zhang Y.-H. Shi B.-F. Yu J.-Q. J. Am. Chem. Soc.  2009,  131:  5072 
    Search in Google Scholar
  • 7a Lazareva A. Daugulis O. Org. Lett.  2006,  8:  5211 
    Search in Google Scholar
  • 7b Shabashov D. Daugulis O. Org. Lett.  2006,  8:  4947 
    Search in Google Scholar
  • 7c Wang D.-H. Wasa M. Giri R. Yu J.-Q. J. Am. Chem. Soc.  2008,  130:  7190 
    Search in Google Scholar
  • 8a Zaitsev VG. Shabashov D. Daugulis O. J. Am. Chem. Soc.  2005,  127:  13154 
    Search in Google Scholar
  • 8b Reddy BVS. Reddy LR. Corey EJ. Org. Lett.  2006,  8:  3391 
    Search in Google Scholar
  • 8c Do H.-Q. Daugulis O. J. Am. Chem. Soc.  2008,  130:  1128 
    Search in Google Scholar
  • 9 Reddy BVS. Ramesh K. Yadav JS. Synlett  2011,  169 
    Thieme Connect
10

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.