Synthesis of 2-Acylbenzothiazoles via the Cu(OTf)₂-Catalyzed Tandem Reaction of β,β-Dihalidestyrenes with 2,2′-Disulfanediyldianilines

Abstract

A new method has been developed for the one-pot construction of 2-acylbenzothiazoles via the Cu(OTf)₂-catalyzed tandem reaction of β,β-dihalidestyrenes with 2,2′-disulfane-diyldianilines. A variety of different dihalidestyrenes and diphenyldisulfanes were efficiently converted into the corresponding 2-acylbenzothiszole derivatives in the presence of Cu(OTf)₂. Most importantly, this protocol allowed for the long chain 1,1-dibromohept-1-ene to be converted into the corresponding 2-hexylbenzo[d]thiazole in moderate yield.

Keywords

Cu(OTf)₂ - dihalidestyrene - diphenyldisulfane - 2-acylbenzothiazole - tandem reaction

• References and Notes

• 1a Dondoni A. Comprehensive Heterocyclic Chemistry II. Vol. 3. Shinkai IE. Pergamon; Glasgow: 1996: 373
• 1b Horton DA, Bourne GT, Smythe ML. Chem. Rev. 2003; 103: 893
• 2a Yao S, Schafer-Hales KJ, Belfield KD. Org. Lett. 2007; 9: 5645
• 2b Rodionov VO, Presolski SI, Gardinier S, Lim YH, Finn MG. J. Am. Chem. Soc. 2007; 129: 12696
• 2c Zajac M, Hrobriák P, Magdolen P, Foltínová P, Zahradník P. Tetrahedron 2008; 64: 10605
• 2d Sahu PK, Sahu PK, Gupta SK, Thavaselvam D, Agarwal DD. Eur. J. Med. Chem. 2012; 54: 366
• 2e Christodoulou MS, Colombo F, Passarella D, Leronimo G, Zuco V, Cesare DM, Zunino F. Bioorg. Med. Chem. 2011; 19: 1649
• 2f Bradshaw TD, Westwell AD. Curr. Med. Chem. 2004; 11: 1009
• 3a Chekler EL. P, Katoch-Rouse R, Kiselyov AS, Sherman D, Ouyang XH, Kim K, Wang Y, Hadari YR, Doody JF. Bioorg. Med. Chem. Lett. 2008; 18: 4344
• 3b Zhang X, Wang BL. Green Chem. 2012; 14: 2141
• 3c Bahrami K, Khodaei MM, Naali F. J. Org. Chem. 2008; 73: 6835
• 3d Misra RS, Barthwal JP, Parmar SS, Singh SP, Stenberg VI. J. Pharm. Sci. 1976; 65: 405
• 4a Marsilje TH, Hedrick MP, Desharnais J, Tavassoli A, Zhang Y, Wilson IA, Benkovicd SJ, Boger DL. Bioorg. Med. Chem. 2003; 11: 4487
• 4b Tsutsumi S, Okonogi T, Shibahara S, Ohuchi S, Hatsushiba E, Patchett AA, Christensen BG. J. Med. Chem. 1994; 37: 3492
• 4c Meltzer-Mats E, Babai-Shani G, Pasternak L, Urisky N, Getter T, Viskind O, Eckel J, Cerasi E, Senderowitz H, Sasson S, Gruzman A. J. Med. Chem. 2013; 56: 5335
• 5 Costanzo MJ, Yabut SC, Almond HR. Jr, Andrade-Gordon P, Corcoran TW, de Garavilla L, Kauffman JA, Abraham WM, Recacha R, Chattopadhyay D, Maryanoff BE. J. Med. Chem. 2003; 46: 3865

For recent paper of synthesis of 2-acylbenzothiazoles, see:
• 6a Park N, Heo Y, Kumar MR, Kim Y, Song KH, Lee S. Eur. J. Org. Chem. 2012; 1984
• 6b Sun YD, Jiang HF, Wu WQ, Zeng W, Wu X. Org. Lett. 2013; 15: 1598
• 6c Fan XS, He Y, Zhang XY, Guo SH, Wang YY. Tetrahedron 2011; 67: 6369
• 6d Mu XJ, Zou JP, Zeng RS, Wu JC. Tetrahedron Lett. 2005; 46: 4345
• 6e Zhu YP, Jia FC, Liu MC, Wu AX. Org. Lett. 2012; 14: 4414
• 6f Yang ZY, Chen X, Wang SZ, Liu JD, Xie K, Wang AW, Tan Z. J. Org. Chem. 2012; 77: 7086
• 6g Fan XS, He Y, Wang YY, Xue ZK, Zhang XY, Wang JJ. Tetrahedron Lett. 2011; 52: 899
• 7 Dieter RK. Tetrahedron 1999; 55: 4177
• 8 Boga C, Stengel R, Abdayem R, Vecchio ED, Forlani L, Todesco PE. J. Org. Chem. 2004; 69: 8903
• 9 Fan XS, He Y, Guo SH, Zhang XY. Aust. J. Chem. 2011; 64: 1578
• 10a Zhu YP, Lian Mi, Jia FC, Liu MC, Yuan JJ, Gao QH, Wu AX. Chem. Commun. 2012; 48: 9086
• 10b Gao QH, Wu X, Jia FC, Liu MC, Zhu YP, Cai Q, Wu AX. J. Org. Chem. 2013; 78: 2792
• 11 Fan XS, He Y, Zhang XY, Guo SH, Wang YY. Tetrahedron 2011; 67: 6369
• 12 Recently, Srogl reported a similar Cu(I) complex-catalyzed methodology of synthesis of 2-acylbenzothiazoles under acidic conditions, see: Hyvl J, Srogl J. Eur. J. Org. Chem. 2010; 2849
• 13 To a Schlenk tube were added a mixture of β,β-dibromo-styrene 1a (0.2 mmol) and 2,2′-disulfanediyldianiline 2a (0.4 mmol), Cu(OTf)₂ (10 mol%), Cs₂CO₃ (2 equiv), and DMSO (2 mL). Then the mixture was stirred at 120 °C for the indicated time until complete consumption of starting material as monitored by TLC and GC–MS analysis. After the reaction was finished, the mixture was washed with brine. The aqueous phase was re-extracted with Et₂O. The combined organic extracts were dried over Na₂SO₄ and concentrated under vacuum, and the resulting residue was purified by silica gel column chromatography (hexane–EtOAc) to afford the target product 3. Benzo[d]thiazol-2-yl(4-methoxyphenyl)methanone (3): white solid; mp 120–122 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.58 (d, J = 9.0 Hz, 2 H), 8.17 (d, J = 8.0 Hz, 1 H), 7.94 (d, J = 8.0 Hz, 1 H), 7.47–7.51 (m, 2 H), 6.98 (d, J = 9.0 Hz, 2 H), 3.85 (s, 3 H). ¹³C NMR (125 MHz, CDCl₃): δ = 183.4, 167.9, 164.4, 153.9, 136.9, 133.8, 127.8, 127.4, 126.8, 125.5, 122.1, 113.9, 55.6. LRMS (EI, 70 eV): m/z (%) = 269 (21) [M⁺], 241 (13), 135 (100), 107 (13), 92 (16), 77 (23).