Download PDF
Synlett 2018; 29(01): 94-98
DOI: 10.1055/s-0036-1588565
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Benzamide Derivatives by the Reaction of Arenes and Isocyanides through a C–H Bond Activation Strategy

Mehdi Khalaj*
a   Young Researchers and Elite Club, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran
,
Mahboubeh Taherkhani
b   Young Researchers and Elite Club, Takestan Branch, Islamic Azad University, Takestan, Iran   Email: khalaj_mehdi@yahoo.com
,
Seyed Mahmoud Mousavi-Safavi
a   Young Researchers and Elite Club, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran
,
Jafar Akbari
a   Young Researchers and Elite Club, Buinzahra Branch, Islamic Azad University, Buinzahra, Iran
› Author Affiliations
Further Information

Publication History

Received: 10 July 2017

Accepted after revision: 19 August 2017

Publication Date:
15 September 2017 (online)

    Permissions and Reprints All articles of this category


Abstract

A carbon–carbon bond formation reaction between isocyanides and benzene derivatives is reported. In contrast to traditional cross-coupling reactions, which require aryl halides or pseudohalides, we use a palladium catalyst to generate the aryl–palladium through C–H bond activation of arenes. This method offers an attractive approach to a range of benzamides from readily accessible benzene derivatives.

Keywords

C–H bond activation - palladium salt - benzamide - isocyanide
 

  • References

  • 1 Shang R. Ilies L. Nakamura E. Chem. Rev. 2017; 117: 9086
    Crossref
  • 2 Labinger JA. Bercaw JE. Nature 2002; 417: 507
    Crossref
  • 3 Wang X. Gensch T. Lerchen A. Daniliuc CG. Glorius F. J. Am. Chem. Soc. 2017; 139: 6506
    CrossrefPubMed
  • 4 Godula K. Sames D. Science 2006; 312: 67
    Crossref
  • 5 Izawa Y. Pun D. Stahl SS. Science 2011; 333: 209
    Crossref
  • 6 Upadhyay NS. Thorat VH. Sato R. Annamalai P. Chuang SH. Cheng CH. Green Chem. 2017; 19: 3219
    Crossref
  • 7 He J. Wasa M. Chan KS. L. Shao Q. Yu JQ. Chem. Rev. 2017; 117: 8754
    Crossref
  • 8 Jia C. Piao D. Oyamada J. Lu W. Kitamura T. Fujiwara Y. Science 2000; 287: 1992
    Crossref
  • 9 Zhang YH. Shi BF. Yu JQ. J. Am. Chem. Soc. 2009; 131: 5027
  • 10 Li R. Jiang L. Lu W. Organometallics 2006; 25: 5973
    Crossref
  • 11 Wu J. Hoang KL. M. Leow ML. Liu XW. Org. Chem. Front. 2015; 2: 502
    Crossref
  • 12 Curto JM. Kozlowski MC. J. Am. Chem. Soc. 2015; 137: 18
    Crossref
  • 13 Liu H. Shi G. Pan S. Jiang Y. Zhang Y. Org. Lett. 2013; 15: 4098
    Crossref
  • 14 Stuart DR. Fagnou K. Science 2007; 316: 1172
    Crossref
  • 15 Huang L. Guo H. Pan L. Xie C. Eur. J. Org. Chem. 2013; 6027
  • 16 Jiang H. Liu B. Li Y. Wang A. Huang H. Org. Lett. 2011; 13: 1028
    CrossrefPubMed
  • 17 Yavari I. Ghazanfarpour-Darjani M. Bayat MJ. Tetrahedron Lett. 2014; 55: 4981
    Crossref
  • 18 Li Y. Cao J. Zhu Q. Zhang X. Shi G. Russ. J. Gen. Chem. 2016; 86: 668
    Crossref
  • 19 Lu F. Chen Z. Li Z. Wang X. Peng X. Li C. Fang L. Liu D. Gao M. Lei A. Org. Lett. 2017; 19: 3954
    CrossrefPubMed
  • 20 Wu J. Hoang KL. M. Leow ML. Liu XW. Org. Chem. Front. 2015; 2: 502
    Crossref
  • 21 Giri R. Liang J. Lei JG. Li JJ. Wang DH. Chen X. Naggar IC. Guo CY. Foxman BM. Yu JQ. Angew. Chem. Int. Ed. 2005; 44: 7420
    Crossref
  • 22 Fujiwara Y. Takaki K. Taniguchi Y. Synlett 1996; 591
    Article in Thieme Connect
  • 23 Brainard MW. Nutt WR. Lee TR. Whitesides GM. Organometallics 1998; 7: 2379
  • 24 Vlaar T. Orru RV. A. Maes BU. W. Ruijter E. J. Org. Chem. 2013; 78: 10469
    CrossrefPubMed
  • 25 Yang F. Song F. Li W. Lan J. You J. RSC Adv. 2013; 3: 9649
    Crossref
  • 26 Typical procedure for the preparation of 3 Pd(OAc)2 (10 mol%), PivOH (0.5 mmol), (NH4)2S2O8 (1.5 mmol), arene (5.0 mmol), TFA (1.0 mL), and diglyme (3.0 mL) were added to a test tube. The mixture was then evacuated and flushed with argon (3 times) and stirred for 30 min at 25 °C. Afterwards, the isocyanide (1.0 mmol) was added by microsyringe. The reaction mixture was then stirred at 110 °C for 28 h and then allowed to cool to room temperature. The crude reaction mixture was diluted with H2O (10 mL) and stirred for 30 min, followed by addition of EtOAc (5 mL) and a saturated NaHCO3 solution (3 mL). The mixture was stirred for an additional 30 min and the two layers were separated. The aqueous layer was extracted with EtOAc (3 × 10 mL). The combined organic layers were dried with MgSO4, filtered, and concentrated in vacuo. The residue was purified by flash column chromatography (silica gel, hexane/EtOAc 3:1) to give the desired product. The spectroscopic data of all known compounds were satisfactory and consistent with those reported in the literature.16–18 tert-Butyl benzoylglycinate (3k) White solid. M.p.: 72–74 °C. Yield: 0.19 g (80%). IR (KBr) (νmax, cm–1): 3245, 3073, 2928, 1734, 1649, 1538, 1332, 1152. 1H NMR (500.1 MHz, CDCl3): δ = 1.67 (s, 9 H, 3 CH3), 4.32 (d, 3 J = 6.1 Hz, 2 H, CH2), 7.55–7.61 (m, 3 H, 3 CH), 7.97 (d, 3 J = 6.6 Hz, 2 H, 2 CH), 8.35 (br d, 3 J = 6.1 Hz, 1 H, NH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 32.1 (3 CH3), 46.9 (CH2), 87.0 (C), 128.9 (2 CH), 129.6 (2 CH), 131.8 (CH), 136.5 (C), 165.1 (CH), 167.3 (C) ppm. MS: m/z (%) = 235 ([M]+, 5), 175 (39), 105 (100), 77 (68), 57 (87). Anal. Calcd for C13H17NO3 (235.28): C, 66.36; H, 7.28; N, 5.95. Found: C, 66.70; H, 7.42; N, 6.13. tert-Butyl (4-methoxybenzoyl)glycinate (3l) Colorless solid. M.p.: 96–98 °C. Yield: 0.24 g (89%). IR (KBr) (νmax, cm–1): 3355, 3034, 2979, 1731, 1635, 1312, 1176. 1H NMR (500.1 MHz, CDCl3): δ = 1.63 (s, 9 H, 3 CH3), 3.79 (s, 3 H, OCH3), 4.26 (d, 3 J = 6.3 Hz, 2 H, CH2), 7.06 (d, 3 J = 6.8 Hz, 2 H, 2 CH), 7.79 (d, 3 J = 6.8 Hz, 2 H, 2 CH), 8.49 (br d, 3 J = 6.3 Hz, 1 H, NH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 34.2 (3 CH3), 46.1 (CH2), 57.0 (OCH3), 85.1 (C), 117.1 (2 CH), 128.2 (C), 130.1 (2 CH), 162.1 (C), 165.6 (CH), 168.0 (C) ppm. MS: m/z (%) = 265 ([M]+, 4), 208 (31), 135 (100), 107 (63), 74 (53), 57 (81). Anal. Calcd for C14H19NO4 (265.31): C, 63.38; H, 7.22; N, 5.28. Found: C, 63.61; H, 7.39; N, 5.49. tert-Butyl (2,4,6-trimethoxybenzoyl)glycinate (3m) Pale yellow solid. M.p.: 156–158 °C. Yield: 0.32 g (98%). IR (KBr) (νmax, cm–1): 3245, 3073, 2928, 1733, 1653, 1538, 1332, 1152. 1H NMR (500.1 MHz, CDCl3): δ = 1.57 (s, 9 H, 3 CH3), 3.78 (s, 3 H, OCH3), 3.83 (s, 6 H, 2 OCH3), 4.24 (d, 3 J = 5.8 Hz, 2 H, CH2), 6.36 (s, 2 H, 2 CH), 8.28 (br d, 3 J = 5.8 Hz, 1 H, NH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 33.1 (3 CH3), 46.4 (CH2), 56.2 (OCH3), 57.4 (2 OCH3), 83.6 (C), 97.8 (2 CH), 118.6 (C), 158.9 (2 C), 161.5 (C), 165.0 (CH), 167.6 (C) ppm. MS: m/z (%) = 325 ([M]+, 13), 268 (24), 195 (100), 167 (65), 131 (56), 57 (87). Anal. Calcd for C16H23NO6 (325.36): C, 59.07; H, 7.11; N, 4.31. Found: C, 59.28; H, 7.25; N, 4.44. tert-Butyl (4-(tert-butyl)benzoyl)glycinate (3n) Colorless solid. M.p.: 89–91 °C. Yield: 0.14 g (47%). IR (KBr) (νmax, cm–1): 3265, 3070, 2967, 1736, 1638, 1544, 1329, 1144. 1H NMR (500.1 MHz, CDCl3): δ = 1.29 (s, 9 H, 3 CH3), 1.60 (s, 9 H, 3 CH3), 4.47 (d, 3 J = 6.4 Hz, 2 H, CH2), 7.38 (d, 3 J = 6.9 Hz, 2 H, 2 CH), 7.79 (d, 3 J = 6.9 Hz, 2 H, 2 CH), 8.32 (br d, 3 J = 6.4 Hz, 1 H, NH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 30.4 (3 CH3), 33.8 (3 CH3), 39.1 (C), 46.9 (CH2), 85.1 (C), 128.1 (2 CH), 128.6 (2 CH), 134.3 (C), 153.2 (C), 165.3 (CH), 167.9 (C) ppm. MS: m/z (%) = 291 ([M]+, 1), 234 (27), 161 (85), 133 (29), 130 (46), 57 (100). Anal. Calcd for C17H25NO3 (291.39): C, 70.07; H, 8.65; N, 4.81. Found: C, 70.29; H, 8.92; N, 4.98. tert-Butyl (1-methyl-1H-indole-3-carbonyl)glycinate (3o) Yellow solid. M.p.: 97–99 °C. Yield: 0.26 g (89%). IR (KBr) (νmax, cm–1): 3231, 3065, 2979, 1739, 1643, 1547, 1344, 1124. 1H NMR (500.1 MHz, CDCl3): δ = 1.56 (s, 9 H, 3 CH3), 3.51 (s, 3 H, CH3), 4.10 (d, 3 J = 6.0 Hz, 2 H, CH2), 7.52–7.60 (m, 3 H, 3 CH), 8.22 (br d, 3 J = 6.0 Hz, 1 H, NH), 8.28 (s, 1 H, CH), 8.40 (d, 3 J = 6.9 Hz, 1 H, CH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 33.1 (3 CH3), 36.9 (CH3), 45.7 (CH2), 83.8 (C), 114.1 (CH), 114.6 (C), 123.1 (CH), 123.4 (CH), 125.8 (CH), 128.2 (C), 134.5 (CH), 138.0 (C), 165.7 (CH), 168.2 (C). MS: m/z (%) = 288 ([M]+, 7), 273 (16), 231 (28), 158 (89), 131 (52), 57 (100) ppm. Anal. Calcd for C16H20N2O3 (288.35): C, 66.65; H, 6.99; N, 9.72. Found: C, 66.83; H, 7.24; N, 9.89. tert-Butyl (2,4,6-trimethylbenzoyl)glycinate (3p) Pale yellow solid. M.p.: 107–109 °C. Yield: 0.07 g (26%). IR (KBr) (νmax, cm–1): 3240, 3043, 2978, 1740, 1641, 1530, 1344, 1141. 1H NMR (500.1 MHz, CDCl3): δ = 1.61 (s, 9 H, 3 CH3), 2.32 (s, 3 H, CH3), 2.38 (s, 6 H, 2 CH3), 4.37 (d, 3 J = 5.6 Hz, 2 H, CH2), 6.91 (s, 2 H, 2 CH), 8.31 (br d, 3 J = 5.6 Hz, 1 H, NH) ppm. 13C NMR (125.7 MHz, CDCl3): δ = 20.7 (2 CH3), 24.1 (CH3), 33.5 (3 CH3), 47.0 (CH2), 83.1 (C), 129.6 (2 CH), 132.3 (2 C), 136.1 (C), 143.8 (C), 165.2 (CH), 167.9 (C) ppm. MS: m/z (%) = 277 ([M]+, 3), 220 (32), 147 (67), 131 (58), 119 (81), 57 (100). Anal. Calcd for C16H23NO3 (277.36): C, 69.29; H, 8.36; N, 5.05. Found: C, 69.53; H, 8.61; N, 5.24.