Synthesis of Thia-Analogues of Calothrixin B Involving FeCl3-Mediated Domino Reaction

Bose Muthu Ramalingam; Nachiappan Dhatchana Moorthy; Elangovan Vellaichamy; Arasambattu K. Mohanakrishnan

doi:10.1055/s-0036-1588072

Synlett, Inhaltsverzeichnis

Synlett 2017; 28(01): 133-137
DOI: 10.1055/s-0036-1588072

letter

Synthesis of Thia-Analogues of Calothrixin B Involving FeCl₃-Mediated Domino Reaction

Bose Muthu Ramalingam

^aDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai-600 Tamil Nadu, India eMail: mohanakrishnan@unom.ac.in eMail: mohan_67@hotmail.com

,

Nachiappan Dhatchana Moorthy

^bDepartment of Biochemistry, University of Madras, Guindy Campus, Chennai-600 Tamil Nadu, India

,

Elangovan Vellaichamy

^bDepartment of Biochemistry, University of Madras, Guindy Campus, Chennai-600 Tamil Nadu, India

,

Arasambattu K. Mohanakrishnan*

^aDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai-600 Tamil Nadu, India eMail: mohanakrishnan@unom.ac.in eMail: mohan_67@hotmail.com

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

The total synthesis of thiacalothrixins, an isostere of the biologically important carbazoloquinone alkaloid calothrixin B, was achieved from ethyl benzo[b]thiophene-2-carboxylate. Alternatively, the multi-step synthesis of thiaisocalothrixins could be achieved from 3-methylbenzo[b]thiophene. A preliminary in vitro cytotoxicity evaluation of the synthesized thia analogues of calothrixins displayed promising potential against cancer cell cultures.

Key words

carbazole alkaloids - calothrixin B - electrocyclization - Lewis acid - quinones

Volltext

Referenzen

References and Notes
1 Goodwin S, Smith AF, Horning EC. J. Am. Chem. Soc. 1959; 81: 1903

2a Miki Y, Hachiken H, Yanase N. J. Chem. Soc., Perkin Trans. 1 2001; 2213
2b Knölker H.-J, Reddy KR. Chem. Rev. 2002; 102: 4303
2c Knölker H.-J, Reddy KR In The Alkaloids . Vol. 65. Cordell GA. Elsevier Science; New York: 2008: 1-430
2d Miller CM, McCarthy FO. RSC Adv. 2012; 2: 8883
2e Schmidt AW, Reddy KR, Knölker H.-J. Chem. Rev. 2012; 112: 3193
2f O’Sullivan EC, Miller CM, Deane FM, McCarthy FO. Studies in Natural Product Chemistry 2013; 189-232

3a Buzdar AU, Hortobagyi GN, Esparza LT, Holmes FA, Ro JS, Fraschini G, Lichtiger B. Oncology 1990; 47: 101
3b Rouesse J, Spielmann M, Turpin F, Le Chavelier T, Azab M, Mondesir JM. Eur. J. Cancer 1993; 6: 856
3c Ohashi M, Oki T. Expert Opin. Ther. Pat. 1996; 6: 1285
3d Kattan J, Durand M, Droz JP, Mahjoubi M, Marino JP, Azab M. Am. J. Clin. Oncol. 1994; 17: 242

4 Rickards RW, Rothschild JM, Willis AC, de Chazal NM, Kirk J, Kirk K, Saliba KJ, Smith GD. Tetrahedron 1999; 55: 13513

5a Bernardo PH, Chai CL. L, Heath GA, Mahon PJ, Smith GD, Waring P, Wilkes BA. J. Med. Chem. 2004; 47: 4958
5b Bernardo PH, Chai CL. L, Le Guen M, Smith GD, Waring P. Bioorg. Med. Chem. Lett. 2007; 17: 82
5c Matsumoto K, Choshi T, Hourai M, Zamami Y, Sasaki K, Abe T, Ishikura M, Hatae N, Iwamura N, Tohyama S, Nobuhiro J, Hibino S. Bioorg. Med. Chem. Lett. 2012; 22: 4762

6 Doan NT, Stewart PR, Smith GD. FEMS Microbiol. Lett. 2001; 196: 135
7 Khan QA, Lu J, Hecht SM. J. Nat. Prod. 2009; 72: 438
8 Chen X, Smith GD, Waring P. J. Appl. Phycol. 2003; 15: 269

9a Kelly TR, Zhao Y, Cavero M, Torneiro M. Org. Lett. 2000; 2: 3735
9b Bernardo PH, Chai CL. L, Elix JA. Tetrahedron Lett. 2002; 43: 2939
9c Bernardo PH, Chai CL. L. J. Org. Chem. 2003; 68: 8906
9d Tohyama S, Choshi T, Matsumoto K, Yamabuki A, Ikegata K, Nobuhiro J, Hibino S. Tetrahedron Lett. 2005; 46: 5263
9e Yamabuki A, Fujinawa H, Choshi T, Tohyama S, Matsumoto K, Ohmura K, Nobuhiro J, Hibino S. Tetrahedron Lett. 2006; 47: 5859
9f Sissouma D, Maingot L, Collet S, Guingant A. J. Org. Chem. 2006; 71: 8434
9g Bernardo PH, Fitriyanto W, Chai CL. L. Synlett 2007; 1935
9h Bennasar M.-L, Roca T, Ferrando F. Org. Lett. 2006; 8: 561
9i McErlean CS. P, Sperry J, Blake AJ, Moody CJ. Tetrahedron 2007; 63: 10963
9j Abe T, Ikeda T, Yanada R, Ishikura M. Org. Lett. 2011; 13: 3356
9k Sissouma D, Collet CS, Guingant AY. Synlett 2004; 2612
9l Abe T, Ikeda T, Choshi T, Hibino S, Hatae N, Toyata E, Yanada R, Ishikura M. Eur. J. Org. Chem. 2012; 5018
9m Ramkumar N, Nagarajan R. J. Org. Chem. 2013; 78: 2802
9n Ramkumar N, Nagarajan R. J. Org. Chem. 2014; 79: 736
9o Bhosale SM, Gawade RL, Puranik VG, Kusurkar RS. Tetrahedron Lett. 2012; 53: 2894
9p Mal DR, Roy J, Biradha K. Org. Biomol. Chem. 2014; 12: 8196
9q Xu S, Ngugen T, Pomilio I, Vitale MC, Velu SE. Tetrahedron 2014; 70: 5928
9r Kaliyaperumal SA, Banerjee S, Kumar SU. K. Org. Biomol. Chem. 2014; 12: 6105
9s Dethe DM, Murhade GM. Eur. J. Org. Chem. 2014; 6953
9t Ramkumar N, Nagarajan R. RSC Adv. 2015; 5: 87838

10a Ramalingam BM, Saravanan V, Mohanakrishnan AK. Org. Lett. 2013; 15: 3726
10b Saravanan V, Ramalingam BM, Mohanakrishnan AK. Eur. J. Org. Chem. 2014; 1266

11a Fujiwara AN, Acton EM, Goodman LJ. J. Heterocycl. Chem. 1968; 5: 853
11b Elmes BC, Swan JM. Aust. J. Chem. 1969; 22: 1963
11c Kano S, Mochizuki N, Hibino S, Shibuya S. J. Org. Chem. 1982; 47: 3566

12 Shi LM, Myers TG, Fan Y, OʼConnor PM, Paul KD, Friend SH, Weinstein SH. Mol. Parmacol. 1998; 53: 241

13a Romagnoli R, Baraldi PG, Carrion MD, Lopez-Cara C, Preti D, Fruttarolo F, Pavani MG, Tabrizi MA, Tolomeo M, Grimaudo S, Cristina AD, Balzarini J, Hadfield JA, Brancale A, Hamle E. J. Med. Chem. 2007; 50: 2273
13b Romagnoli R, Baraldi PG, Lopez-Cara C, Preti D, Tabrizi MA, Balzarini J, Basseetto M, Brancale A, Fu X.-H, Gao Y, Li J, Zhang S.-Z, Hamel E, Bortolozzi R, Basso G, Viola G. J. Med. Chem. 2013; 56: 9296

14a Jarak I, Kralj M, Šuman L, Pavlolić G, Dogan J, Piantanida I, Žinić M, Pavelić K, Karminski-Zamola G. J. Med. Chem. 2005; 48: 2346
14b Ester K, Hranjec M, Piantanida I, Ćaleta I, Jarak I, Pavelić K, Kralji M, Karminski-Zamola G. J. Med. Chem. 2009; 52: 2482

15 Kutsunugi Y, Kawai S, Nakashima T, Kawai T. New J. Chem. 2009; 33: 1368
16 Matsunaga N, Kaku T, Itoh F, Tanaka T, Hara T, Miki H, Iwasaki M, Aono T, Yamaoka M, Kusaka M, Tasaka A. Bioorg. Med. Chem. Lett. 2004; 12: 2251
17 Bauer I, Knölker H.-J. Chem. Rev. 2015; 115: 3170
18 Representative Procedure for the Preparation of Thiacalothrixin B (23a) To a solution of enamine 22a (300 mg, 0.8 mmol) in dry DMF (20 mL), FeCl₃ (520 mg, 3.2 mmol) was added. The reaction mixture was refluxed for 3 h under N₂ atmosphere. It was then poured over crushed ice (50 g) containing concd HCl (1 mL). The crude product was filtered and dried. It was then purified by flash column chromatography on silica gel (230–420 mesh, n-hexane–CH₂Cl₂ = 9:1 to 1:1) to afford thiacalothrixin B (23a) as a red-orange solid (160 mg, 65%); mp 260–262 °C. IR (film): 1651, 1519, 1258, 1092 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 9.81 (s, 1 H), 9.60 (d, J = 8.7 Hz, 1 H), 8.87 (d, J = 7.8 Hz, 1 H), 8.22 (d, J = 8.1 Hz, 1 H), 7.98 (d, J = 7.5 Hz, 1 H), 7.90 (t, J = 7.5 Hz, 1 H), 7.81 (t, J = 7.8 Hz, 1 H), 7.66–7.57 (m, 2 H) ppm. ¹³C NMR (75 MHz, CDCl₃): δ = 182.9, 180.3, 152.1, 148.7, 148.2, 142.4, 135.8, 133.6, 132.9, 132.1, 130.7, 130.4, 128.8, 127.7, 127.5, 127.3, 124.7, 123.0, 122.7 ppm. DEPT 135: δ = 148.2, 132.1, 130.7, 130.4, 128.8, 127.7, 127.5, 127.3, 123.0 ppm. HRMS (EI): m/z cacld for C₁₉H₉NO₂S [M⁺]: 315.0354; found: 315.0354.

Zusatzmaterial

Supporting Information