Synthesis 2017; 49(07): 1597-1602
DOI: 10.1055/s-0036-1588375
paper
© Georg Thieme Verlag Stuttgart · New York

H2SO4-Mediated Intramolecular Cyclization of N-Arylated Homoallylamines: A Solvent-Free, Atom- and Step-Economical Synthesis of Tetrahydro-1-benzazepines

Hua-Shuai Gao
School of Chemistry and Chemical Engineering, and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu, P. R. of China   Email: lmzhao@jsnu.edu.cn
,
Fei Dou
School of Chemistry and Chemical Engineering, and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu, P. R. of China   Email: lmzhao@jsnu.edu.cn
,
Ai-Li Zhang
School of Chemistry and Chemical Engineering, and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu, P. R. of China   Email: lmzhao@jsnu.edu.cn
,
Rui Sun
School of Chemistry and Chemical Engineering, and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu, P. R. of China   Email: lmzhao@jsnu.edu.cn
,
Li-Ming Zhao*
School of Chemistry and Chemical Engineering, and Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou 221116, Jiangsu, P. R. of China   Email: lmzhao@jsnu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 07 October 2016

Accepted after revision: 21 November 2016

Publication Date:
09 December 2016 (online)


Abstract

The biologically important tetrahydro-1-benzazepine skeleton was conveniently constructed from N-arylated homoallylamines through H2SO4-mediated intramolecular cyclization. The advantages of this transformation include mild reaction conditions, experimental simplicity, its solvent- and metal-free, atom- and step-economical nature, and the use of a readily available, cheap, and nontoxic mediator.

Supporting Information

 
  • References


    • For reviews, see:
    • 1a Majumdar KC, Chattopadhyay B, Maji PK, Chattopadhyay SK, Samanta S. Heterocycles 2010; 81: 795
    • 1b Majumdar KC, Debnath P, De N, Roy B. Curr. Org. Chem. 2011; 15: 1760
    • 1c Nag S, Batra S. Tetrahedron 2011; 67: 8959
    • 1d Vo C.-VT, Bode JW. J. Org. Chem. 2014; 79: 2809

      For selected examples of tetrahydro-1-benzazepines, see:
    • 2a Kondo K, Ogawa H, Shinohara T, Kurimura M, Tanada Y, Kan K, Yamashita H, Nakamura S, Hirano T, Yamamura Y, Mori T, Tominaga M, Itai A. J. Med. Chem. 2000; 43: 4388
    • 2b Johnson PD, Aristoff PA, Zurenko GE, Schaadt RD, Yagi BH, Ford CW, Hamel JC, Stapert D, Moerman JK. Bioorg. Med. Chem. Lett. 2003; 13: 4197
    • 2c Yea CM, Allan CE, Ashworth DM, Barnett J, Baxter AJ, Broadbridge JD, Franklin RJ, Hampton SL, Hudson P, Horton JA, Jenkins PD, Penson AM, Pitt GR. W, Riviere P, Robson PA, Rooker DP, Semple G, Sheppard A, Haigh RM, Roe MB. J. Med. Chem. 2008;  51:  8124 
    • 2d Annedi SC, Ramnauth J, Cossette M, Maddaford SP, Dove P, Rakhit S, Andrews JS, Porreca F.  Bioorg. Med. Chem. Lett. 2012;  22:  2510
    • 3a Milkiewicz KL, Aimone LD, Albom MS, Angeles TS, Chang H, Grobelny JV, Husten J, LoSardo C, Miknyoczki S, Murthy S, Rolon-Steele D, Underiner TL, Weinberg LR, Worrell CS, Zeigler KS, Dorsey BD. Bioorg. Med. Chem. 2011; 19: 6274
    • 3b Weinberg LR, Albom MS, Angeles TS, Husten J, Lisko JG, McHugh RJ, Milkiewicz KL, Murthy S, Ott GR, Theroff JP, Tripathy R, Underiner TL, Zificsak CA, Dorsey BD. Bioorg. Med. Chem. Lett. 2011; 21: 164
  • 4 He Y, Chang HM, Lau YK, Cui YX, Wang RJ, Mak TC. W, Wong HN. C, Lee CM. J. Chem. Soc., Perkin Trans. 1 1990; 3359
    • 5a Manabe S, Takayanagi H, Nishino C. J. Chem. Ecol. 1983; 9: 533
    • 5b Ohloff G, Giersch W, Pickenhagen W, Furrer A, Frei B. Helv. Chim. Acta 1985; 68: 2022
  • 6 For a review, see: Burkhard JA, Wuitschik G, Rogers-Evans M, Mueller K, Carreira EM. Angew. Chem. Int. Ed. 2010; 49: 9052
  • 7 For a review, see: Balfour JA, Goa KL. Drugs 1991; 42: 511
  • 8 For a review, see: Wilson S, Argyropoulos S. Drugs 2005; 65: 927

    • For reviews, see:
    • 9a Katritzky AR, Rachwal S, Rachwal B. Tetrahedron 1996; 52: 15031
    • 9b Sridharan V, Suryavanshi PA, Menendez JC. Chem. Rev. 2011; 111: 7157
    • 9c Nammalwar B, Bunce RA. Molecules 2014; 19: 204

    • For selected examples, see:
    • 9d Vargas ML, Rozo W, Kouznetsov V. Heterocycles 2000; 53: 785
    • 9e Fujita K, Yamamoto K, Yamaguchi R. Org. Lett. 2002; 4: 2691
    • 9f Ortiz-Marciales M, Rivera LD, De Jesus M, Espinosa S, Benjamin JA, Casanova OE, Figueroa IG, Rodriguez S, Correa W. J. Org. Chem. 2005; 70: 10132
    • 9g Ren H, Zanger M, McKee J. Synth. Commun. 2006; 36: 355
    • 9h Cho H, Iwama Y, Sugimoto K, Mori S, Tokuyama H. J. Org. Chem. 2010; 75: 627
    • 9i Sirvent JA, Foubelo F, Yus M. J. Org. Chem. 2014; 79: 1356
    • 10a Prostakov NS, Kuznetsov VV, Stashenko EE. Khim. Geterotsikl. Soedin. 1989; 1514
    • 10b Okabe K, Muratake H, Natsume M. Tetrahedron 1991; 47: 8559
    • 10c Kouznetsov V, Urbina J, Palma A, Lopez S, Devia C, Enriz R, Zacchino S. Molecules 2000; 5: 428
    • 10d Urbina JM, Cortes JC. G, Palma A, Lopez SN, Zacchino SA, Enriz RD, Ribas JC, Kouznetzov VV. Bioorg. Med. Chem. 2000; 8: 691
    • 11a Cossy J, Poitevin C, Pardo DG, Peglion J.-L, Dessinges A. J. Org. Chem. 1998; 63: 4554
    • 11b Giacobbe SA, Di Fabio R. Tetrahedron Lett. 2001; 42: 2027
    • 11c Qadir M, Cobb J, Sheldrake PW, Whittall N, White AJ. P, Hii KK, Horton PN, Hursthouse MB. J. Org. Chem. 2005; 70: 1545
    • 11d Sole D, Mariani F, Fernandez I, Sierra MA. J. Org. Chem. 2012; 77: 10272
  • 12 Zhao L.-M, Zhang S.-Q, Jin H.-S, Wan L.-J, Dou F. Org. Lett. 2012; 14: 886
    • 13a Zhao L.-M, Jin H.-S, Wan L.-J, Zhang L.-M. J. Org. Chem. 2011; 76: 1831
    • 13b Zhao L.-M, Zhang S.-Q, Dou F, Sun R. Org. Lett. 2013; 15: 5154
    • 13c Zhao L.-M, Wan L.-J, Zhang S.-Q, Sun R, Ma F.-Y. Tetrahedron 2013; 69: 7970
    • 13d Jin H.-S, Zhang S.-Q, Sun R, Dou F, Zhao L.-M. RSC Adv. 2014; 4: 21810
    • 14a Zhao L.-M, Dou F, Sun R, Zhang A.-L. Synlett 2014; 25: 1431
    • 14b Zhao L.-M, Zhang A.-L, Gao H.-S, Zhang J.-H. J. Org. Chem. 2015; 80: 10353
    • 14c Zhao L.-M, Zhang A.-L, Zhang J.-H, Gao H.-S, Zhou W. J. Org. Chem. 2016; 81: 5487