BULLETIN OF THE
Article
An Efficient Synthesis of Dihydrobenzo[c]azepines
KOREAN CHEMICAL SOCIETY
H. Allouchi, J. Martinez, F. Lamaty, Eur. J. Org. Chem.
F. Wu, X. Yi, H. Wang, W. Chen, Chem. Commun. 2015,
51, 6862.
2007, 201; (b) P. Ribiere, V. Declerck, Y. Nedellec,
N. Yadav-Bhatnagar, J. Martinez, F. Lamaty, Tetrahedron
2006, 62, 10456; (c) B. Bradshaw, P. Evans, J. Fletcher,
A. T. L. Lee, P. G. Mwashimba, D. Oehlrich, E. J. Thomas,
R. H. Davies, B. C. P. Allen, K. J. Broadley, A. Hamrouni,
C. Escargueil, Org. Biomol. Chem. 2008, 6, 2138;
(d) J. Gonzalez, A. Gomez, I. Funes-Ardoiz, J. Santamaria,
D. Sampedro, Chem. Eur. J. 2014, 20, 7061; (e) P. Hasebein,
K. Aulinger, D. Schepmann, B. Wunsch, Tetrahedron 2013,
69, 4552; (f ) H. Cao, T. O. Vieira, H. Alper, Org. Lett. 2011,
13, 11; (g) K. Okuro, H. Alper, Synlett 2012, 23, 2531.
2. For the synthesis and biological activity of polycyclic benzo
[c]azepine derivatives, see: (a) P. Hewawasam, Y. Tu,
T. W. Hudyma, X. Zhang, R. G. Gentles, J. F. Kadow,
N. A. Meanwell, Tetrahedron Lett.. 2014, 55, 1148 and fur-
ther references cited therein; (b) P. Cheng, D. L. J. Clive,
J. Org. Chem. 2012, 77, 3348; (c) T. Novak, Z. Mucsi,
B. Balazs, L. Keresztely, G. Blasko, M. Nyerges, Synlett
2010, 2411; (d) H. S. Lee, K. H. Kim, S. H. Kim, J. N. Kim,
Tetrahedron Lett. 2012, 53, 497; (e) H. S. Lee, S. H. Kim,
T. H. Kim, J. N. Kim, Tetrahedron Lett. 2008, 49, 1773; (f )
H. S. Lee, S. H. Kim, S. Gowrisankar, J. N. Kim, Tetrahe-
dron 2008, 64, 7183; (g) S. Gowrisankar, K. Y. Lee,
J. N. Kim, Bull. Korean Chem. Soc. 2005, 26, 1112;
(h) S. H. Ko, K.-J. Lee, J. Heterocycl. Chem. 2004, 41, 613;
(i) C. M. Marson, J. H. Pink, D. Hall, M. B. Hursthouse,
A. Malik, C. Smith, J. Org. Chem. 2003, 68, 792;
(j) R. Reinhard, M. Glaser, R. Neumann, G. Maas, J. Org.
Chem. 1997, 62, 7744; (k) C. M. Marson, J. H. Pink,
C. Smith, Tetrahedron Lett. 1995, 36, 8107.
7. For selected examples on montmorillonite K-10-assisted
organic synthesis, see:(a) J. Yu, J. W. Lim, S. Y. Kim,
J. Kim, J. N. Kim, Tetrahedron Lett. 2015, 56, 1432 and fur-
ther references cited therein; (b) B. S. Kumar,
A. Dhakshinamoorthy, K. Pitchumani, Catal. Sci. Technol.
2014, 4, 2378; (c) N. Kaur, D. Kishore, J. Chem. Pharm. Res.
2012, 4, 991; (d) K. Kaneda, Synlett 2007, 999;
(e) D. A. Borkin, M. Puscau, A. Carlson, A. Solan,
K. A. Wheeler, B. Torok, R. Dembinski, Org. Biomol. Chem.
2012, 10, 4505.
8. For Pictet–Spengler reaction using montmorillonite K-10, see:
(a) H. Cho, F. Torok, B. Torok, Green Chem. 2014, 16,
3623; (b) Y. F. Wang, Z. B. Song, C. X. Chen, J. S. Peng,
Sci. China: Chem. 2010, 53, 562; (c) A. Kulkarni, M. Abid,
B. Torok, X. Huang, Tetrahedron Lett. 2009, 50, 1791.
9. For Pictet–Spengler reaction using heteropolyacids (HPAs),
see:(a) G. P. Romanelli, D. M. Ruiz, J. C. Autino,
H. E. Giaccio, Mol. Diversity 2010, 14, 803; (b) G. Pasquale,
D. Ruiz, J. Autino, G. Baronetti, H. Thomas, G. Romanelli,
C. R. Chim 2012, 15, 758; (c) R. Pingaew,
S. Prachayasittikul, S. Ruchirawat, V. Prachayasittikul, Chin.
Chem. Lett. 2013, 24, 941.
10. For the synthesis of starting materials, see: (a) K. H. Kim,
S. H. Kim, H. J. Lee, J. N. Kim, Adv. Synth. Catal. 2013,
355, 1977; (b) K. H. Kim, J. W. Lim, H. R. Moon, J. N. Kim,
Bull. Korean Chem. Soc. 2014, 35, 3254; (c) J. Yu,
H. R. Moon, J. W. Lim, J. N. Kim, Bull. Korean Chem. Soc.
2015, 36, 203; (d) D. Basavaiah, T. Satyanarayana, Chem.
Commun. 2004, 32.
3. For general reviews on MBH reaction, see: (a) D. Basavaiah,
A. J. Rao, T. Satyanarayana, Chem. Rev. 2003, 103, 811;
(b) D. Basavaiah, B. S. Reddy, S. S. Badsara, Chem. Rev.
2010, 110, 5447; (c) V. Singh, S. Batra, Tetrahedron 2008,
64, 4511; (d) J. N. Kim, K. Y. Lee, Curr. Org. Chem. 2002,
6, 627; (e) K. Y. Lee, S. Gowrisankar, J. N. Kim, Bull.
Korean Chem. Soc. 2005, 26, 1481; (f ) S. Gowrisankar,
H. S. Lee, S. H. Kim, K. Y. Lee, J. N. Kim, Tetrahedron
2009, 65, 8769; (g) M. Shi, F.-J. Wang, M.-X. Zhao, Y. Wei,
The Chemistry of the Morita-Baylis-Hillman Reaction, RSC
Publishing, Cambridge, 2011.
4. For the synthesis of 2-benzoxepines from MBH adducts, see:
(a) D. Basavaiah, D. S. Sharada, A. Veerendhar, Tetrahedron
Lett. 2004, 45, 3081; (b) B. Das, A. Majhi, J. Banerjee,
N. Chowdhury, H. Holla, K. Harakishore, U. S. Murty, Chem.
Pharm. Bull. 2006, 54, 403; (c) M. Bakthadoss,
N. Sivakumar, A. Devaraj, Tetrahedron Lett. 2015, 56, 4980.
5. For reviews on Pictet–Spengler reaction, see: (a) E. D. Cox,
J. M. Cook, Chem. Rev. 1995, 95, 1797; (b) J. Stockigt,
A. P. Antonchick, F. Wu, H. Waldmann, Angew. Chem. Int.
Ed. 2011, 50, 8538; (c) E. L. Larghi, M. Amongero,
A. B. J. Bracca, T. S. Kaufman, ARKIVOC 2005, xii, 98;
(d) E. L. Larghi, T. S. Kaufman, Eur. J. Org. Chem.
2011, 5195.
11. The use of phosphotungstic acid hydrate (H3[PW12O40],
100%, w/w), as one of HPAs, also afforded 2a in refluxing
1,2-dichloroethane in good yield (91%) for 2 h. The use of
paraformaldehyde or formalin showed almost similar reactiv-
ity to that of 1,3,5-trioxane. In addition, the reaction of 1a and
1,3,5-trioxane in CH2Cl2 in the presence of H2SO4 (1.0 equiv)
also afforded 2a in good yield (92%) even at room tempera-
ture for 2 h. As noted above, 2a could be synthesized in high
yield irrespective of acid catalyst (K-10, HPAs, and H2SO4)
and formaldehyde sources (1,3,5-trioxane, paraformaldehyde,
and formalin). Among the conditions we selected the combi-
nation of montmorillonite K-10/1,3,5-trioxane and carried out
the other entries.
12. (a) J. Yu, S. Lee, H. R. Moon, J. N. Kim, Bull. Korean Chem.
Soc. 2015, 36, 1900; (b) J. W. Lim, K. H. Kim, S. H. Kim,
J. N. Kim, Tetrahedron Lett. 2012, 53, 5449; (c) J. W. Lim,
K. H. Kim, S. H. Kim, J. N. Kim, Tetrahedron 2014, 70,
6831; (d) J. W. Lim, S. H. Kim, J. Kim, J. N. Kim, Bull.
Korean Chem. Soc. 2015, 36, 1351; (e) L. Zhang,
S. A. Kozmin, J. Am. Chem. Soc. 2004, 126, 10204.
13. For dihydrothieno[3,2-c]azepine derivatives, see: (a) Z. Dong,
C.-H. Liu, Y. Wang, M. Lin, Z.-X. Yu, Angew. Chem. Int.
Ed. 2013, 52, 14157; (b) W. Zhang, F. Ning, L. Varadi,
D. E. Hibbs, J. A. Platts, M. Nyerges, R. J. Anderson,
P. W. Groundwater, Tetrahedron 2014, 70, 3621.
6. For Pictet–Spengler type reaction of N-sulfonyliminium ion,
see: (a) M. Hellal, S. Singh, G. D. Cuny, Tetrahedron 2012,
68, 1674; (b) R. Pingaew, S. Prachayasittikul, S. Ruchirawat,
V. Prachayasittikul, Med. Chem. Res. 2013, 22, 267;
(c) C. C. Silveira, C. R. Bernardi, A. L. Braga,
T. S. Kaufman, Tetrahedron Lett. 1999, 40, 4969; (d) X. Ma,
14. For
dihydrofuro[2,3-c]azepine
derivatives,
see:
(a) K. Knobloch, M. Keller, W. Eberbach, Eur. J. Org. Chem.
2001, 3313; (b) P. A. Jacobi, C. A. Blum, R. W. DeSimone,
U. E. S. Udodong, J. Am. Chem. Soc. 1991, 113, 5384;
Bull. Korean Chem. Soc. 2016, Vol. 37, 680–684
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