PDF herunterladen
Synlett 2012; 23(8): 1209-1212
DOI: 10.1055/s-0031-1290919
letter
© Georg Thieme Verlag Stuttgart · New York

A Convenient Synthesis of Functionalized Tricyclic Frameworks Containing an Azocine Moiety

Issa Yavari*
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran, Fax: +98(21)82883455   eMail: yavarisa@modares.ac.ir
,
Samereh Seyfi
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran, Fax: +98(21)82883455   eMail: yavarisa@modares.ac.ir
› Institutsangaben
Weitere Informationen

Publikationsverlauf

Received: 13. Februar 2012

Accepted after revision: 06. März 2012

Publikationsdatum:
26. April 2012 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik


Abstract

Tetrahydro-3a,8b-dihydroxy-oxoindeno[1,2-b]pyrroles, prepared from ninhydrin and enamines, are subjected to intramolecular Wittig reactions to afford dihydro-1H-furo[2′,3′:2,3]cyclopenta[1,2-b]pyrroles. These fused 5,5-ring systems undergo Et3N-mediated fragmentation to afford tetrahydrobenzo[c]furo[3,2-e]-­azocines in good yields.

Key words

acetylenic ester - ninhydrin - multicomponent reactions - intramolecular Wittig reaction - azocine
 

  • References and Notes

  • 1 Illuminati G, Mandolini L. Acc. Chem. Res. 1981; 14: 95
    Crossref
  • 2 Yet L. Chem. Rev. 2000; 100: 2963
  • 3 Ma S, Gu Z. J. Am. Chem. Soc. 2006; 128: 4942
    Crossref
  • 4 Evans PA, Holmes AB. Tetrahedron 1991; 47: 9131
    Crossref
  • 5 Kuehne ME, Cowen SD, Xu F, Borman LS. J. Org. Chem. 2001; 66: 5303
    Crossref
  • 6 Oda O, Ohnuma T, Ban Y. J. Org. Chem. 1984; 49: 953
    Crossref
  • 7 Donati D, Fusi S, Ponticelli F. Eur. J. Org. Chem. 2002; 4211
  • 8 Oniciu DC. Comprehensive Heterocyclic Chemistry III . Katrizky AR, Ramsden CA, Scriven EF. V, Taylor RJ. K. Elsevier; Oxford: 2008
    Google Scholar
  • 9 Voskressensky LG, Kulikova LN, Borisova TN, Varlamov AV. Adv. Heterocycl. Chem. 2008; 96: 81
  • 10 Voskressensky LG, Borisova TN, Kulikova LV, Varlamov AV, Catto M, Altomare C, Carotti A. Eur. J. Org. Chem. 2004; 3128
  • 11 Akhter L, Brown RT, Moorcroft D. Tetrahedron Lett. 1978; 19: 4137
    Crossref
  • 12 Valencia E, Fajardo V, Freyer AJ, Shamma M. Tetrahedron Lett. 1985; 26: 993
    Crossref
  • 13 Evans PA, Holmes AB. Tetrahedron 1991; 47: 9131
    Crossref
  • 14 Tadic D, Linders JT. M, Flippen-Anderson JL, Jacobson AE, Rice KC. Tetrahedron 2003; 59: 4603
    Crossref
  • 15 Yavari I, Khalili G. Synlett 2010; 1862
    Artikel in Thieme Connect
  • 16 Yavari I, Souri S, Sirouspour M, Bayat MJ. Synlett 2009; 1921
    Artikel in Thieme Connect
  • 17 Yavari I, Adib M, Sayahi MH. Tetrahedron Lett. 2002; 43: 2927
    Crossref
  • 18 Yavari I, Seyfi S, Nematpour M, Hossaini Z. Helv. Chim. Acta 2010; 93: 1413
    Crossref
  • 19 General Procedure for the Preparation of Compounds 3 To a solution of 2 (2 mmol) and Ph3P (0.51 g, 2 mmol) in CH2Cl2 (10 mL) was added a solution of DMAD 1 (0.28 g, 2 mmol) in CH2Cl2 (4 mL). After stirring for 10 min at –5 °C, the reaction mixture was allowed to reach r.t. After completion of the reaction, as indicated by TLC (hexane–EtOAc = 5:1), the solvent was evaporated under reduced pressure to leave a residue that was purified by column chromatography (SiO2; hexane–EtOAc = 5:1) to afford pure desired products 3. Selected Spectroscopic Data Compound 3a: white powder; mp 220–225 °C; yield 0.82 g (80%). IR (KBr): νmax = 3390, 2947, 1727, 1578, 1433, 1353, 1257, 1009, 745 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.56 (3 H, s, MeO), 3.61 (3 H, s, MeO), 3.65 (3 H, s, MeO), 3.70 (3 H, s, MeO), 5.22 (1 H, s, OH), 5.98 (1 H, s, CH), 7.33 (1 H, d, 3 J = 7.3 Hz, CH), 7.35–7.41 (5 H, m, 5 CH), 7.49 (1 H, t, 3 J = 7.5 Hz, CH), 7.58 (1 H, t, 3 J = 8.1 Hz, CH), 8.07 (1 H, d, 3 J = 7.3 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 51.3 (MeO), 51.8 (MeO), 52.7 (MeO), 53.4 (MeO), 89.4 (CH), 93.9 (C), 99.6 (C), 105.5 (C), 120.9 (C), 124.5 (CH), 124.7 (CH), 127.8 (CH), 128.1 (2 CH), 128.5 (2 CH), 130.6 (CH), 135.2 (C), 136.1 (CH), 136.9 (C), 146.5 (C), 152.1 (C), 155.2 (C), 161.7 (C=O), 162.4 (C=O), 164.0 (C=O), 171.8 (C=O). MS (EI): m/z (%) = 521 (15) [M+], 491 (20), 444 (30), 262 (35), 208 (15), 77 (100), 59 (32). Anal. Calcd (%) for C27H23NO10 (521.47): C, 62.19; H, 4.45; N, 2.69. Found: C, 62.22; H, 4.49; N, 2.74. Compound 3b: yellow powder; mp 212–217 °C; yield 0.90 g (85%). IR (KBr): νmax = 3436, 2943, 1709, 1570, 1451, 1280, 1212, 1131, 1013 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.50 (3 H, s, MeO), 3.62 (3 H, s, MeO), 3.80 (3 H, s, MeO), 3.81 (3 H, s, MeO), 4.71 (1 H, d, 2 J = 15.7 Hz, CH), 4.86 (1 H, s, OH), 5.01 (1 H, d, 2 J = 15.7 Hz, CH), 6.00 (1 H, s, CH), 7.24 (1 H, d, 3 J = 7.3 Hz, CH), 7.25–7.43 (5 H, m, 5 CH), 7.44 (1 H, t, 3 J = 7.5 Hz, CH), 7.47 (1 H, t, 3 J = 8.1 Hz, CH), 8.06 (1 H, d, 3 J = 7.3 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 47.1 (CH2N), 51.0 (MeO), 51.8 (MeO), 52.6 (MeO), 52.8 (MeO), 89.4 (CH), 93.9 (C), 99.6 (C), 105.5 (C), 120.9 (C), 124.5 (CH), 126.5 (CH), 127.8 (CH), 128.1 (2 CH), 128.5 (CH), 132.0 (CH), 132.5 (CH), 134.2 (C), 134.3 (CH), 136.9 (C), 146.5 (C), 152.1 (C), 155.2 (C), 161.7 (C=O), 162.4 (C=O), 164.0 (C=O), 171.8 (C=O). MS (EI): m/z (%) = 535 (15) [M+], 476 (20), 444 (32), 262 (35), 208 (15), 91 (100), 59 (30). Anal. Calcd (%) for C28H25NO10 (535.50): C, 62.80; H, 4.71; N, 2.62. Found: C, 62.83; H, 4.75; N, 2.70. Compound 3c: cream powder; mp 224–230 °C; yield 0.84 g (74%). IR (KBr): νmax = 3418, 2943, 1707, 1571, 1449, 1346, 1272, 1202, 1131, 1705 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.53 (3 H, s, MeO), 3.56 (3 H, s, MeO), 3.72 (3 H, s, MeO), 3.75 (3 H, s, MeO), 4.94 (1 H, d, 2 J = 8.3 Hz, CH), 4.96 (1 H, s, OH), 5.09 (1 H, d, 2 J = 8.3 Hz, CH), 6.01 (1 H, s, CH), 7.23 (1 H, d, 2 J = 7.3 Hz, CH), 7.24 (1 H, t, 3 J = 7.3 Hz, CH), 7.27 (1 H, t, 3 J = 7.5 Hz, CH), 7.47 (2 H, m, 2 CH), 7.67 (2 H, t, 3 J = 7.5 Hz, 2 CH), 8.07 (1 H, d, 3 J = 7.3 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 47.1 (CH2N), 51.0 (MeO), 51.8 (MeO), 52.6 (MeO), 52.8 (MeO), 89.5 (CH), 94.0 (C), 100.1 (C), 105.4 (C), 120.9 (C), 124.0 (CH), 124.5 (CH), 124.7 (CH), 127.8 (CH), 128.1 (CH), 128.5 (2 CH), 132.5 (CH), 132.6 (C), 132.9 (CH), 134.8 (C), 146.6 (C), 152.0 (C), 155.2 (C), 161.7 (C=O), 162.0 (C=O), 164.0 (C=O), 171.8 (C=O). MS (EI): m/z (%) = 569 (15) [M+], 539 (20), 444 (32), 262 (35), 208 (15), 126 (100), 59 (30). Anal. Calcd (%) for C28H24NClO10 (569.94): C, 59.01; H, 4.24; N, 2.46. Found: C, 59.22; H, 4.29; N, 2.52. Compound 3d: white powder; mp 209–214 °C; yield 1.04 g (88%). IR (KBr): νmax = 3429, 2930, 1730, 1447, 1260, 753 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.55 (3 H, s, MeO), 3.62 (3 H, s, MeO), 3.80 (3 H, s, MeO), 3.81 (3 H, s, MeO), 3.83 (3 H, s, MeO), 4.64 (1 H, d, 2 J = 15.7 Hz, CH), 4.91 (1 H, s, OH), 4.92 (1 H, d, 2 J = 15.7 Hz, CH), 5.99 (1 H, s, CH), 6.87 (2 H, d, 3 J = 7.3 Hz, 2 CH), 7.21 (1 H, d, 3 J = 7.3 Hz, CH), 7.25 (2 H, d, 3 J = 7.3 Hz, 2 CH), 7.35 (1 H, t, 3 J = 7.5 Hz, CH), 7.43 (1 H, t, 3 J = 8.1 Hz, CH), 8.00 (1 H, d, 3 J = 7.3 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 46.5 (CH2N), 51.0 (MeO), 51.9 (MeO), 52.7 (MeO), 52.9 (MeO), 55.3 (MeO), 89.3 (CH), 93.9 (C), 99.3 (C), 105.6 (C), 113.9 (C), 120.8 (CH), 124.2 (CH), 126.5 (CH), 128.4 (2 CH), 128.5 (2 CH), 128.9 (CH), 129.4 (C), 146.5 (C), 152.1 (C), 131.9 (C), 155.3 (C), 159.3 (C), 161.7 (C=O), 162.5 (C=O), 164.1 (C=O), 171.8 (C=O). MS (EI): m/z (%) = 595 (15) [M+], 535 (20), 444 (28), 262 (32), 208 (15), 122 (100), 59 (30). Anal. Calcd (%) for C29H27NO11 (595.52): C, 61.59; H, 4.81; N, 2.48. Found: C, 61.62; H, 4.91; N, 2.52. Compound 3e: yellow powder; mp 219–223 °C; yield 0.68 g (76%). IR (KBr): νmax = 3407, 2964, 1730, 1577, 1440, 1262, 1178, 1045 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.02 (3 H, s, MeN), 3.56 (3 H, s, MeO), 3.61 (3 H, s, MeO), 3.65 (3 H, s, MeO), 3.70 (3 H, s, MeO), 5.22 (1 H, s, OH), 5.98 (1 H, s, CH), 7.33 (1 H, d, 3 J = 7.3 Hz, CH), 7.43 (1 H, t, 3 J = 7.3 Hz, CH), 7.76 (1 H, t, 3 J = 7.5 Hz, CH), 7.99 (1 H, d, 3 J = 8.1 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 31.8 (MeN), 51.3 (MeO), 51.8 (MeO), 52.7 (MeO), 53.4 (MeO), 89.4 (CH), 93.9 (C), 105.5 (C), 120.9 (C), 124.5 (CH), 127.8 (CH), 128.5 (CH), 130.6 (CH), 135.2 (C), 136.9 (C), 146.5 (C), 152.1 (C), 155.2 (C), 161.7 (C=O), 162.4 (C=O), 164.0 (C=O), 171.8 (C=O). MS (EI): m/z (%) = 459 (15) [M+], 429 (22), 444 (32), 262 (34), 208 (12), 59 (30), 15 (100). Anal. Calcd (%) for C22H21NO10 (459.40): C, 57.52; H, 4.61; N, 3.05. Found: C, 57.4; H, 4.6; N, 3.0. Compound 3f: yellow powder; mp 190–199 °C; yield 0.78 g (80%). IR (KBr): νmax = 3407, 1715, 1693, 1633, 1685, 1556, 1509, 1441, 1368, 1076 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 1.02 (3 H, t, 3 J = 7.1 Hz, Me), 1.56 (2 H, m, CH2), 2.55 (2 H, t, 3 J = 7.3 Hz, CH2), 3.67 (3 H, s, MeO), 3.70 (3 H, s, MeO), 3.76 (3 H, s, MeO), 3.77 (3 H, s, MeO), 5.26 (1 H, s, OH), 5.98 (1 H, s, CH), 7.47 (1 H, t, 3 J = 7.5 Hz, CH), 7.50 (1 H, t, 3 J = 7.3 Hz, CH), 7.73 (1 H, d, 3 J = 7.5 Hz, CH), 7.84 (1 H, d, 3 J = 8.1 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 11.2 (Me), 22.2 (CH2), 44.3 (CH2N), 51.3 (MeO), 51.8 (MeO), 52.7 (MeO), 53.4 (MeO), 89.4 (CH), 89.9 (C), 91.6 (C), 105.5 (C), 120.9 (C), 124.5 (CH), 124.7 (CH), 127.8 (CH), 128.1 (CH), 145.0 (C), 146.7 (C), 151.7 (C), 152.1 (C), 161.7 (C=O), 162.4 (C=O), 164.0 (C=O), 171.8 (C=O). MS (EI): m/z (%) = 487 (15) [M+], 457 (19), 444 (30), 262 (32), 208 (13), 59 (30), 43 (100). Anal. Calcd (%) for C24H25NO10 (487.45): C, 59.14; H, 5.17; N, 2.87. Found: C, 59.4; H, 5.2; N, 2.9
  • 20 General Procedure for the Preparation of Compounds 4 To a stirred solution of 3 (1 mmol) in EtOH (15 mL) at 50 °C, Et3N (0.010 g, 10 mol%) was added, and stirring was continued for an additional 5 h (TLC monitoring). The solvent was evaporated under reduced pressure, and the resulting residue recrystallized from EtOH–hexane to give compound 4. Compound 4a: cream crystals; mp 152–157 °C; yield 0.40 g (75%). IR (KBr): νmax = 3435, 1749, 1666, 1571, 1559, 1474, 1195, 1159 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.58 (3 H, s, MeO), 3.63 (3 H, s, MeO), 3.66 (3 H, s, MeO), 3.71 (3 H, s, MeO), 4.69 (1 H, d, 2 J = 11.9 Hz, CH), 5.48 (1 H, d, 2 J = 11.9 Hz, CH), 6.97 (1 H, d, 3 J = 7.3 Hz, CH), 7.38–7.68 (5 H, m, 5 CH), 7.65 (2 H, t, 3 J = 7.5 Hz, 2 CH), 8.06 (1 H, d, 3 J = 8.1 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 45.8 (CH), 52.1 (MeO), 52.2 (MeO), 52.6 (MeO), 53.0 (MeO), 62.5 (CH), 121.8 (CH), 123.4 (C), 125.8 (C), 127.1 (2 CH), 128.1 (2 CH), 128.5 (2 CH), 129.4 (CH), 130.0 (C), 131.5 (C), 132.6 (CH), 137.1 (C), 147.0 (C), 157.0 (C), 167.7 (C=O), 168.4 (C=O), 169.5 (C=O), 170.2 (C=O), 172.4 (C=O). MS (EI): m/z (%) = 521 (15) [M+], 491 (20), 339 (30), 262 (35), 182 (15), 77 (100), 59 (32). Anal. Calcd (%) for C27H23NO10 (521.47): C, 62.19; H, 4.45; N, 2.69. Found: C, 62.50; H, 4.49; N, 2.81. Compound 4b: pale yellow crystals; mp 150–155 °C; yield 0.42 g (78%). IR (KBr): νmax = 3436, 1709, 1570, 1451, 1280, 1212, 1131, 710 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.51 (3 H, s, MeO), 3.65 (3 H, s, MeO), 3.78 (3 H, s, MeO), 3.90 (3 H, s, MeO), 4.04 (1 H, d, 2 J = 15.1 Hz, CH), 4.29 (1 H, d, 2 J = 12.3 Hz, CH), 5.12 (1 H, d, 2 J = 15.1 Hz, CH), 5.22 (1 H, d, 2 J = 12.3 Hz, CH), 7.11 (1 H, d, 3 J = 7.2 Hz, CH), 7.26 (1 H, d, 3 J = 7.0 Hz, CH), 7.42–7.46 (2 H, m, 2 CH), 7.47–7.52 (3 H, m, 3 CH), 7.54–7.67 (2 H, m, 2 CH). 13C NMR (125.7 MHz, CDCl3): δ = 45.2 (CH), 45.4 (CH2N), 52.1 (MeO), 52.4 (MeO), 52.6 (MeO), 52.7 (MeO), 60.6 (CH), 121.4 (CH), 121.5 (CH), 123.4 (C), 126.1 (C), 126.9 (CH), 127.0 (CH), 127.5 (2 CH), 127.9 (CH), 128.8 (CH), 129.3 (C), 130.1 (C), 134.1 (C), 136.5 (C), 141.3 (C), 146.8 (C), 156.8 (C=O), 157.2 (C=O), 162.6 (C=O), 168.1 (C=O), 171.0 (C=O). MS (EI): m/z (%) = 535 (15) [M+], 455 (20), 396 (30), 278 (100), 199 (50), 183 (60), 86 (70). Anal. Calcd (%) for C28H25NO10 (535.50): C, 62.80; H, 4.71; N, 2.62. Found: C, 62.92; H, 4.82; N, 2.71. Compound 4c: cream crystals; mp 148–154 °C; yield 0.43 g (76%). IR (KBr): νmax = 3444, 2951, 1736, 1658, 1436, 1308, 1183, 1054, 738 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.58 (3 H, s, MeO), 3.68 (3 H, s, MeO), 3.77 (3 H, s, MeO), 3.91 (3 H, s, MeO), 4.23 (1 H, d, 2 J = 12.0 Hz, CH), 4.37 (1 H, d, 2 J = 15.5 Hz, CH), 5.23 (1 H, d, 2 J = 15.7 Hz, CH), 5.30 (1 H, d, 2 J = 12.1 Hz, CH), 7.08 (1 H, d, 2 J = 8.1 Hz, CH), 7.18 (1 H, d, 3 J = 7.3 Hz, CH), 7.30 (1 H, t, 3 J = 7.5 Hz, CH), 7.44 (1 H, t, 3 J = 8.1 Hz, CH), 7.50 (2 H, m, 2 CH), 7.67 (1 H, t, 3 J = 7.5 Hz, CH), 7.69 (1 H, t, 3 J = 8.1 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 43.2 (CH), 45.4 (CH2N), 52.2 (MeO), 52.4 (MeO), 52.7 (MeO), 52.8 (MeO), 60.7 (CH), 121.7 (CH), 126.3 (CH), 126.5 (CH), 127.1 (C), 127.9 (C), 128.1 (C), 128.2 (CH), 129.4 (CH), 129.7 (CH), 130.3 (CH), 131.6 (CH), 131.7 (C), 131.9 (C), 133.9 (C), 141.4 (C), 146.9 (C), 157.2 (C=O), 162.6 (C=O), 167.6 (C=O), 168.0 (C=O), 172.0 (C=O). MS (EI): m/z (%) = 569 (15) [M+], 534 (32), 454 (20), 277 (100), 199 (40), 125 (35), 69 (35). Anal. Calcd (%) for C28H24NClO10 (569.94): C, 59.01; H, 4.24; N, 2.46. Found: C, 59.21; H, 4.28; N, 2.52. Compound 4d: cream crystals; mp 144–149 °C; yield 0.51 g (86%). IR (KBr): νmax = 3423, 1703, 1563, 1451, 1341, 1268, 1115, 753 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.57 (3 H, s, MeO), 3.61 (3 H, s, MeO), 3.66 (3 H, s, MeO), 3.77 (3 H, s, MeO), 3.93 (3 H, s, MeO), 4.29 (1 H, d, 2 J = 12.2 Hz, CH), 4.36 (1 H, d, 2 J = 15.2 Hz, CH), 5.21 (1 H, d, 2 J = 15.2 Hz, CH), 5.25 (1 H, d, 2 J = 12.1 Hz, CH), 6.74 (1 H, t, 3 J = 7.3 Hz, CH), 7.03 (1 H, d, 3 J = 7.3 Hz, CH), 7.25 (1 H, t, 3 J = 7.3 Hz, CH), 7.43–7.54 (3 H, m, 3 CH), 7.64 (1 H, d, 3 J = 7.1 Hz, CH), 7.67 (1 H, d, 3 J = 7.3 Hz, CH). 13C NMR (125.7 MHz, CDCl3): δ = 45.3 (CH), 45.7 (CH2N), 52.1 (MeO), 52.3 (MeO), 52.6 (MeO), 52.7 (MeO), 54.8 (MeO), 62.2 (CH), 113.6 (2 CH), 126.3 (CH), 126.9 (C), 127.9 (C), 128.2 (2 CH), 129.2 (CH), 130.0 (C), 131.6 (CH), 131.7 (2 CH), 131.9 (C), 132.7 (C), 134.2 (C), 146.8 (C), 146.9 (C), 159.0 (C=O), 162.6 (C=O), 168.2 (C=O), 171.0 (C=O). MS (EI): m/z (%) = 595 (15) [M+], 407 (20), 329 (28), 383 (32), 208 (15), 182 (100), 59 (30). Anal. Calcd for C29H27NO11 (595.52): C, 61.59; H, 4.81; N, 2.48. Found: C, 61.65; H, 4.93; N, 2.51
  • 21 Burnett AM. N, Johnson CK. Oak Ridge National Laboratory Report ORNL-6895. Oak Ridge National Laboratory; Tennessee: 1996
    Google Scholar