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Synlett 2010(6): 955-961  
DOI: 10.1055/s-0029-1219550
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Easy Access to Novel Spiro-Fused Pyrrolo Benzo[b]thiophene 1,1-Dioxide Derivatives via 1,3-Dipolar Cycloaddition Using Benzo[b]thiophene 1,1-Dioxide

Neelakandan Vidhya Lakshmi, Prakasam Thirumurugan, Chinnappan Jayakumar, Paramasivan T. Perumal*
Organic Chemistry Division, Central Leather Research Institute, Adyar, Chennai 600020, India
Fax: +91(44)24911589; e-Mail: ptperumal@gmail.com;
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Publikationsverlauf

Received 30 December 2009
Publikationsdatum:
26. Februar 2010 (online)

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Abstract

A series of spirooxindoles containing tri- and tetracyclic fused pyrrolo benzo[b]thiophene 1,1-dioxide derivatives was synthesized regioselectively via a multicomponent 1,3-dipolar cyclo­addition of isatin, benzo[b]thiophene 1,1-dioxide and sarcosine or l-proline in methanol under reflux condition. Also a series of spiro frameworks having tri- and tetracyclic fused pyrrolo benzo[b]thiophene 1,1-dioxide derivatives was synthesized from ninhydrin, 11H-indeno[1,2-b]quinoxalin-11-one and acenaphthene-quinone using benzo[b]thiophene 1,1-dioxide as a dipolarophile. The methodology affords high yields of products in short reaction time.

Key words

spirooxindoles - azomethine ylide - multicomponent ­reaction - benzo[b]thiophene 1,1-dioxide - dipolarophile

    References and Notes

  • 1a Tsuge O. Kanemasa S. Advances in Heterocyclic Chemistry   Vol. 45:  Katritzky AR. Academic; San Diego: 1989.  p.231 
    Google Scholar
  • 1b 1,3-Dipolar Cycloaddition Chemistry   Vol. 1:  Padwa A. Wiley; New York: 1984. 
    Google Scholar
  • 1c 1,3-Dipolar Cycloaddition Chemistry   Vol. 2:  Padwa A. Wiley; New York: NY, 1984. 
    Google Scholar
  • 1d Grigg R. Sridharan V. Advances in Cycloaddition   Vol. 3:  Curran DP. Jai; London: 1993.  p.161 
    Google Scholar
  • 1e Shi F. Mancuso R. Larock RC. Tetrahedron Lett.  2009,  50:  4067 
    Google Scholar
  • 2a Nair V. Suja TD. Tetrahedron  2007,  63:  12247 
    Google Scholar
  • 2b Nájera CN. Sansano JM. Angew. Chem.  2005,  117:  6428 
    Google Scholar
  • 2c Zhang W. Lu Y. Geib S. Org. Lett.  2004,  7:  2269 
    Google Scholar
  • 2d Coldham I. Hufton R. Chem. Rev.  2005,  105:  2765 
    Google Scholar
  • 2e Ghandi M. Yari A. Rezaei SJT. Taheri A. Tetrahedron Lett.  2009,  50:  4724 
    Google Scholar
  • 2f Belskaya NP. Bakulev VA. Deryabina TG. Subbotina JO. Kodess MI. Dehaen W. Toppet S. Robeyns K. Meervelt LV. Tetrahedron  2009,  65:  7662 
    Google Scholar
  • 2g Karthikeyan K. Kumar RS. Muralidharan D. Perumal PT. Tetrahedron Lett.  2009,  50:  7175 
    Google Scholar
  • 2h Ahrendt KA. Williams RM. Org. Lett.  2004,  6:  4539 
    Google Scholar
  • 2i Nyerges M. Gajdics L. Szöllösy A. Töke L. Synlett  1999,  111 
    Google Scholar
  • 3a Kim P. Tsuruda JM. Olmstead MM. Eisenberg S. Kurth MJ. Tetrahedron Lett.  2002,  43:  3963 
    Google Scholar
  • 3b Svoboda J. Štádler M. Jandera A. Panajotova V. Kuchar M. Collect. Czech. Chem. Commun.  2000,  65:  1082 
    Google Scholar
  • 3c Viola G. Salvador A. Vedaldi D. Fortunato E. Disarò S. Basso G. Queiroz M.-JRP. J. Photochem. Photobiol. B: Biol.  2006,  82:  105 
    Google Scholar
  • 3d Allen D. Callaghan O. Cordier FL. Dobson DR. Harris JR. Hotten TM. Owton WM. Rathwell RE. Wood VA. Tetrahedron Lett.  2004,  45:  9645 
    Google Scholar
  • 3e Galiano S. Erviti O. Pérez S. Moreno A. Juanenea L. Aldana I. Monge A. Bioorg. Med. Chem. Lett.  2004,  14:  597 
    Google Scholar
  • 3f Innocenti A. Villar R. Martinez-Merino V. Gil MJ. Scozzafava A. Vullo A. Supuran CT. Bioorg. Med. Chem. Lett.  2005,  15:  4872 
    Google Scholar
  • 4 Von Fischer U. Schneider F. Helv. Chim. Acta  1980,  63:  1719 
    CrossrefGoogle Scholar
  • 5 Bened A. Durand R. Pioch D. Geneste P. Guimon C. Guillouzo GP. Declercq J.-P. Germain G. Briard P. Rambaud J. Roques R. J. Chem. Soc., Perkin Trans. 2  1984,  1 
    CrossrefGoogle Scholar
  • 6a Bened A. Durand R. Pioch D. Geneste P. Declercq J.-P. Germain G. Rambaud J. Roques R. Guimon C. Guillouzo GP. J. Org. Chem.  1982,  47:  2461 
    Google Scholar
  • 6b Albini FM. Ceva P. Mascherpa A. Albini E. Caramella P. Tetrahedron  1982,  38:  3629 
    Google Scholar
  • 7 Sauter F. Büyük G. Jordis U. Monatsh. Chem.  1974,  105:  869 
    CrossrefGoogle Scholar
  • 8 Malatesti N. Boa AN. Clark S. Westwood R. Tetrahedron Lett.  2006,  47:  5139 
    CrossrefGoogle Scholar
  • 9a Kotha BS. Deb CA. Lahiri K. Synthesis  2009,  0165 
    Google Scholar
  • 9b Augustine T. Kanakam CC. Vithiya SM. Ramkumar V. Tetrahedron Lett.  2009,  50:  5906 
    Google Scholar
  • 9c Trost BM. Brennan MK. Synthesis  2009,  3003 
    Google Scholar
  • 10a Basavaiah D. Reddy RK. Org. Lett.  2007,  9:  57 
    Google Scholar
  • 10b Kumar RR. Perumal S. Senthilkumar P. Yogeeswari P. Sriram D. Eur. J. Med. Chem.  2009,  44:  3821 
    Google Scholar
  • 11a Hilton ST. Ho TCT. Pljevaljcic G. Jones K. Org. Lett.  2000,  2:  2639 
    Google Scholar
  • 11b Smet M. Oosterwijck CV. Hecke KV. Meervelt LV. Vandendriessche A. Dehaen W. Synlett  2004,  2388 
    Google Scholar
  • 12 Shanmugam P. Viswambharan B. Madhavan S. Org. Lett.  2007,  9:  4095 
    CrossrefGoogle Scholar
  • 13 Shanmugam P. Viswambharan B. Selvakumar K. Madhavan S. Tetrahedron Lett.  2008,  49:  2611 
    CrossrefGoogle Scholar
  • 14 Murugan R. Anbazhagan S. Narayanan SS. Eur. J. Med. Chem.  2009,  44:  3272 
    CrossrefGoogle Scholar
  • 15a Babu TH. Joseph AA. Muralidharan D. Perumal PT. Tetrahedron Lett.  2010,  51:  994 
    Google Scholar
  • 15b Lakshmi NV. Thirumurugan P. Perumal PT. Tetrahedron Lett.  2010,  51:  1064 
    Google Scholar
  • 16 Sureshbabu AR. Raghunathan R. Satiskumar BK. Tetrahedron Lett.  2009,  50:  2818 
    CrossrefGoogle Scholar
17

Crystallographic data for compound 4c in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplemental publication no. CCDC 759326. Copies of the data can be obtained, free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(1223)336033 or email: deposit@ccdc.cam.ac.uk].

18

Typical Experimental Procedure for 4a: A mixture of isatin (1a; 1.0 mmol), sarcosine (2; 1.2 mmol), and benzo[b]thiophene 1,1-dioxide (3; 1.1 mmol) in MeOH was refluxed for 60 min and cooled to r.t. The solid formed in the reaction mixture was filtered, dried and recrystallized from EtOH to obtain the pure product in good yield (85%).
Spectral Data of Compound 4a (Table 1, Entry 1): white solid; mp 234-236 ˚C; R f 0.25 (50% EtOAc-PE). IR (KBr): 3150, 3074, 1708, 1619, 1467, 1301, 1153, 1124, 755 cm-¹. ¹H NMR (500 MHz, DMSO-d 6): δ = 1.91 (s, 3 H, Me), 3.52 (d, 1 H, J = 9.9 Hz, H1), 3.69-3.72 (m, 1 H, H2), 4.30 (t, 1 H, J = 7.6 Hz, H3), 4.53 (d, 1 H, J = 9.2 Hz, H4), 5.77 (d, 1 H, J = 7.6 Hz, ArH), 6.48 (d, 1 H, J = 8.4 Hz, ArH), 6.58 (t, 1 H, J = 7.6 Hz, ArH), 6.80 (d, 1 H, J = 7.7 Hz, ArH), 7.11 (t, 1 H, J = 7.7 Hz, ArH), 7.33 (t, 1 H, J = 7.6 Hz, ArH), 7.48 (t, 1 H, J = 7.7 Hz, ArH), 7.74 (d, 1 H, J = 7.7 Hz, ArH), 10.54 (br s, 1 H, NH, D2O exch). ¹³C NMR (125 MHz, DMSO-d 6): δ = 35.1, 52.1, 52.3, 62.1, 74.7, 110.2, 121.1, 121.5, 125.8, 127.0, 129.9, 130.1, 130.3, 132.9, 135.7, 140.3, 143.3, 179.2. MS (ESI, LCQ-MS): m/z = 341 [M + H]+. Anal. Calcd for C18H16N2O3S: C, 63.51; H, 4.74; N, 8.23. Found: C, 63.57; H, 4.72; N, 8.31.

19

Typical Experimental Procedure for 12: A mixture of ninhydrin 9 (1.0 mmol), sarcosine (2; 1.2 mmol), and benzo[b]thiophene 1,1-dioxide (3; 1.1 mmol) in MeOH was refluxed for 45 min and cooled to r.t. The solid formed in the reaction mixture was filtered, dried and recrystallized from EtOH to obtain the pure product in good yield (87%).
Spectral Data of Compound 12 (Table 3, Entry 1): yellow solid; mp 252-254 ˚C; R f 0.25 (50% EtOAc-PE). IR (KBr): 1739, 1706, 1588, 1307, 1268, 1152, 1124, 768 cm-¹. ¹H NMR (500 MHz, DMSO-d 6): δ = 2.07 (s, 3 H, Me), 3.61-3.67 (m, 2 H, H1, H2), 4.35-4.37 (m, 1 H, H3), 4.72 (d, 1 H, J = 9.9 Hz, H4), 6.68 (d, 1 H, J = 7.7 Hz, ArH), 7.42 (t, 1 H, J = 6.9 Hz, ArH), 7.50 (t, 1 H, J = 7.7 Hz, ArH), 7.72 (d, 1 H, J = 7.7 Hz, ArH), 7.83 (d, 1 H, J = 7.7 Hz, ArH), 8.02-8.07 (m, 3 H, ArH). ¹³C NMR (125 MHz, DMSO-d 6): δ = 35.7, 52.1, 54.1, 61.6, 76.5, 121.7, 123.4, 123.9, 128.4, 130.5, 133.6, 134.8, 137.9, 138.1, 140.2, 140.6, 141.9, 199.3, 202.3. MS (ESI, LCQ-MS): m/z = 354 [M + H]+. Anal. Calcd for C19H15NO4S: C, 64.58; H, 4.28; N, 3.96. Found: C, 64.52; H, 4.32; N, 3.90.

20

Typical Experimental Procedure for 15: A mixture of ninhydrin 9 (1.0 mmol), l-proline (6; 1.2 mmol), and benzo[b]thiophene 1,1-dioxide (3; 1.1 mmol) in MeOH was refluxed for 60 min and cooled to r.t. The solid formed in the reaction mixture was filtered, dried and recrystallized from EtOH to obtain the pure product in good yield (87%).
Spectral Data of Compound 15 (Table 3, Entry 4): yellow solid; mp 234-236 ˚C; R f 0.25 (50% EtOAc-PE). IR (KBr): 3435, 2958, 1713, 1591, 1286, 1143, 757 cm-¹. ¹H NMR (500 MHz, DMSO-d 6): δ = 1.64-1.66 (m, 1 H, CH), 1.90-1.95 (m, 1 H, CH), 2.06-2.10 (m, 1 H, CH), 2.45-2.47 (m, 1 H, CH), 2.54 (t, 1 H, J = 6.9 Hz, CH), 2.98-3.01 (m, 1 H, CH), 4.29-4.32 (m, 1 H, H3), 4.42-4.44 (m, 1 H, H1), 5.05 (d, 1 H, J = 9.9 Hz, H4), 6.60 (d, 1 H, J = 8.4 Hz, ArH), 7.33 (t, 1 H, J = 7.6 Hz, ArH), 7.44 (t, 1 H, J = 7.7 Hz, ArH), 7.69 (d, 1 H, J = 8.4 Hz, ArH), 7.77 (d, 1 H, J = 7.7 Hz, ArH), 7.98 (t, 1 H, J = 7.7 Hz, ArH), 8.03 (t, 1 H, J = 6.9 Hz, ArH), 8.13 (d, 1 H, J = 7.7 Hz, ArH). ¹³C NMR (125 MHz, DMSO-d 6): δ = 24.9, 28.9, 48.8, 50.6, 67.2, 69.2, 75.6, 122.1, 124.2, 124.7, 126.2, 130.4, 134.4, 134.8, 137.5, 138.2, 140.3, 141.4, 141.7, 196.2, 197.4. MS (ESI, LCQ-MS): m/z = 380 [M + H]+. Anal. Calcd for C21H17NO4S: C, 66.48; H, 4.52; N, 3.69. Found: C, 66.52; H, 4.58; N, 3.71.