Stereoselective Synthesis of Novel 2-Alkenyl-2,3,4,5-tetrahydro-1,4-epoxy-1-benzazepines and 2-Alkenyl-2,3,4,5-tetrahydro-1H-1-benzazepin-4-ols

Abstract

New series of polyfunctionalized 2,3,4,5-tetrahydro-1,4-epoxy-1-benzazepines and 2,3,4,5-tetrahydro-1H-1-benzazepin-4-ols substituted at C2 with 2-methylprop-1-enyl, (E)-styryl, and (E)-pent-1-enyl were synthesized starting from the corresponding N-alkenyl-substituted [prenyl, trans-cinnamyl, (E)-hex-2-enyl] 2-allylanilines by a three-step sequence consisting of selective oxidation of aromatic secondary amines, intramolecular nitrone–olefin 1,3-dipolar cycloaddition, and reductive cleavage. The intramolecular 1,3-dipolar cycloaddition is stereoselective favoring the exo-cycloadducts (ratio exo/endo 2–3:1). The stereochemistry was determined by exhaustive NMR analysis and X-ray diffraction.

Key words

1,3-dipolar cycloaddition - 2,3,4,5-tetrahydro-1,4-epoxy-1-benzazepines - 2,3,4,5-tetrahydro-1H-1-benzazepin-4-ols - reductive cleavage - nitrogen heterocycles

• References

• 1 Hegedus LS, McKearin JM. J. Am. Chem. Soc. 1982; 104: 2444
• 2 Larock RC, Pace P, Yang H, Russell CE, Cacchi S, Fabrizi G. Tetrahedron 1998; 54: 9961
• 3 Benali O, Miranda MA, Tormos R. Eur. J. Org. Chem. 2002; 2317
• 4 Lira R, Wolfe JP. J. Am. Chem. Soc. 2004; 126: 13906
• 5 Ney JE, Hay MB, Yang Q, Wolfe JP. Adv. Synth. Catal. 2005; 347: 1614
• 6 Bertrand MB, Wolfe JP. Tetrahedron 2005; 61: 6447
• 7 Michael FE, Cochran BM. J. Am. Chem. Soc. 2006; 128: 4246
• 8 Correa A, Tellitu I, Dominguez E, SanMartin R. J. Org. Chem. 2006; 71: 8316
• 9 Hegedus LS, Allen GF, Waterman EL. J. Am. Chem. Soc. 1976; 98: 2674
• 10 Hegedus LS, Allen GF, Bozell JJ, Waterman EL. J. Am. Chem. Soc. 1978; 100: 5800
• 11 Hegedus LS, Allen GF, Olsen DJ. J. Am. Chem. Soc. 1980; 102: 3583
• 12 Yip K, Yang M, Law K, Zhu N, Yang D. J. Am. Chem. Soc. 2006; 128: 3130
• 13 Sherman ES, Chemler SR, Tan TB, Gerlits O. Org. Lett. 2004; 6: 1573
• 14 Sherman ES, Fuller PH, Kasi D, Chemler SR. J. Org. Chem. 2007; 72: 3896
• 15 Zeng W, Chemler SR. J. Am. Chem. Soc. 2007; 129: 12948
• 16 Fuller PH, Chemler SR. Org. Lett. 2007; 9: 5477
• 17 Zabawa TP, Kasi D, Chemler SR. J. Am. Chem. Soc. 2005; 127: 11250
• 18 Zabawa TP, Chemler SR. Org. Lett. 2007; 9: 2035
• 19 Anastasiou D, Jackson WR. Aust. J. Chem. 1992; 45: 21
• 20 Larock RC, Hightower TR, Hasvold LA, Peterson KP. J. Org. Chem. 1996; 61: 3584
• 21 Bennasar M, Roca T, Monerris M, García-Díaz D. Tetrahedron Lett. 2005; 46: 4035
• 22 Bennasar M, Roca T, Monerris M, García-Díaz D. J. Org. Chem. 2006; 71: 7028
• 23 Mondal P, Thander L, Chattopadhyay SK. Tetrahedron Lett. 2012; 53: 1328
• 24 Ali BE, Okuro K, Vasapollo G, Alper H. J. Am. Chem. Soc. 1996; 118: 4264
• 25 Ye F, Alper H. Adv. Synth. Catal. 2006; 348: 1855
• 26 Touzani R, Alper H. J. Mol. Catal. A: Chem. 2007; 227: 197
• 27 Qadir M, Cobb J, Sheldrake P, Whittall N, White A, Hii K, Horton P, Hursthouse M. J. Org. Chem. 2005; 70: 1545
• 28 Sato T, Ishida S, Ishibashi H, Ikeda M. J. Chem. Soc., Perkin Trans. 1 1991; 353
• 29 Ikeda M, Obata K, Oka J, Ishibashi H, Sato T. Heterocycles 1997; 44: 203
• 30 Fujiwara T, Kato Y, Takeda T. Heterocycles 2000; 52: 147
• 31 Organ M, Xu J, N’Zemba B. Tetrahedron Lett. 2002; 43: 8177
• 32 Palma A, Jaimes-Barajas J, Kouznetsov VV, Stashenko E, Bahsas A, Amaro-Luis J. Synlett 2004; 2721
• 33 Gómez-Ayala SL, Stashenko E, Palma A, Bahsas A, Amaro-Luis JM. Synlett 2006; 14: 2275
• 34 Yépez AF, Palma A, Stashenko E, Bahsas A, Amaro-Luis JM. Tetrahedron Lett. 2006; 47: 5825
• 35 Acosta LM, Palma A, Bahsas A. Tetrahedron 2010; 66: 8392
• 36 Palma A, Yépes AF, Leal SM, Coronado CA, Escobar P. Bioorg. Med. Chem. Lett. 2009; 19: 2360
• 37 Gómez-Ayala S, Castrillón JA, Palma A, Leal SM, Escobar P, Bahsas A. Bioorg. Med. Chem. 2010; 18: 4721
• 38 Murahashi SI, Mitsui H, Shiota T, Tsuda T, Watanabe S. J. Org. Chem. 1990; 55: 1736
• 39 Acosta LM, Bahsas A, Palma A, Cobo J, Low JN, Glidewell C. Acta Crystallogr., Sect. C 2008; 64: o514
• 40 Acosta LM, Palma A, Bahsas A, Cobo J, Glidewell C. Acta Crystallogr., Sect. C 2010; 66: o206
• 41 Acosta LM, Palma A, Bahsas A, Cobo J, Glidewell C. Acta Crystallogr., Sect. C 2010; 66: o209