Directed ortho metalation - Cross coupling connections. Remote lateral metalation - Cyclization of 2-Imino-2'-methyl biaryls to 9- aminophenanthrenes. A synthesis of the alkaloid piperolactam C+

Tetrahedron Letters

Volumn 39, Issue 9, 1998, Pages 961-964

  Benesch, Lisbeth ^a   Bury, Paul ^a   Guillaneux, Denis ^a   Houldsworth, Stephen ^a   Wang, X ^a   Snieckus, Victor ^a  

^a UNIVERSITY OF WATERLOO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

9 AMINOPHENANTHRENE DERIVATIVE; ALKALOID; BENZYLISOQUINOLINE DERIVATIVE; LITHIUM DERIVATIVE; PHENANTHRENE DERIVATIVE; PIPEROLACTAM C; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; DRUG SYNTHESIS; STEREOSPECIFICITY; SYNTHESIS;

EID: 0032567907     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10670-0     Document Type: Article

References (33)

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5. (4) Wang, X.; Snieckus, V. Tetrahedron Lett. 1991, 32, 4879.
6. 2 displacment: (a) Altiparmakian, R.H.; Braithwaite, R.S.W. J. Chem. Soc., C1967, 1818;
7. (b) Bergstrom, F.W.; Horning, C.H. J. Org. Chem. 1946, 11, 334;
8. (c) Mirsadeghi, S.; Prasad, G.K.B.; Whittaker, N.; Hiakker, D.R. J. Org. Chem. 1989, 54, 3091.
9. By Curtius rearrangement of the acyl azide: (d) Goldberg, M.A.; Ordas, E.P.; Carsch, G. J. Am. Chem. Soc. 1947, 69, 260;
10. (e) Newman, M.S.; Blum, J. J. Am. Chem. Soc. 1964, 86, 1835;
11. (f) Mosby, W.L. J. Org. Chem. 1959, 24, 421;
12. (g) Newman, M.S.; Kosak, A.I. J. Org. Chem. 1949, 14, 375. By nitration-reduction: Bavin, P.M.G.; Dewar, M.J.S. J. Chem. Soc. 1956, 164.
13. (g) Newman, M.S.; Kosak, A.I. J. Org. Chem. 1949, 14, 375. By nitration-reduction: Bavin, P.M.G.; Dewar, M.J.S. J. Chem. Soc. 1956, 164.
14. 3: (i) Yasuda, M.; Harada, T.; Ansho, Y.; Shima, K. Bull. Chem. Soc. Jpn . 1993, 66, 1451.
15. (j) Denis, J.N.; Krief, A. Tetrahedron 1979, 35, 2901.
16. By Friedel-Crafts reaction of 2-phenyl phenylacetonitrile: (k) Bradsher, C.K.; Little, E.D.; Beavers, D.J. J. Am. Chem. Soc. 1956, 78, 2153.
17. (6) (a) Desai, S.J.; Prabhu, B.R.; Mulchandani, N.B. Phytochemistry 1988, 27, 1511.
18. (b) Olsen, C.E.; Tyaggi, O.D.; Boll, P.M.; Hussaini, F.A.; Parmar, V.S.; Sharma, N.K.; Taneja, P.; Jain, S.C. Phytochemistry 1993, 33, 518.
19. (c) Desai, S.J.; Chaturvedi, R.N.; Badheka, L.P.; Mulchandani, N.B. Indian J. Chem. 1989, 28B, 775.
20. For approaches towards this and related classes of alkaloids, see: (d) Estevez, J.C.; Villaverde, M.C.; Estevez, R.J.; Castedo, L. Tetrahedron Lett. 1992, 33, 5145.
21. (e) Castedo, L.; Guitian, E.; Saa, J.M.; Suau, R. Heterocycles, 1982, 19, 279.
22. (f) Castedo, L.; Guitian, E.; Saa, J.M.; Suau, R. Tetrahedron Lett. 1982, 23, 457.
23. (g) Estevez, J.C.; Estevez, R.J.; Guitian, E.; Villaverde, M.C.; Castedo, L. Tetrahedron Lett., 1989, 30, 5785.
24. (7) Compounds of general structure 6 were prepared by Suzuki cross coupling of readily available ortAo-bromo-benzaldehydes or -benzonitriles with orrAo-tolyl boronic acids, which, in turn, were obtained via lithium/halogen exchange of the corresponding bromotoluenes. The methoximes and N′,N′-dimethylhydrazones were prepared in high yields from the corresponding aldehydes by standard procedures. Benesch, L. M.Sc. Thesis, University of Waterloo, 1995.
25. 5a 133-135 °C.
26. (9) Treatment of the methoximine (Table 1, entry 5) with 2.5 equiv of LiDEA, gave the corresponding nitrile as the only isolable product in 73% yield. It was converted into 9-aminophenanthrene in 60% yield (21% recovered starting material) using 1.2 equiv of LiDEA. The LDA-mediated conversion of an aromatic N,N-dimethylhydrazone into the corresponding nitrile is precedented, see Mao, Y.-L.; Boekelheide, V. J. Org. Chem. 1980, 45, 2746.
27. 2 afforded the C-10 acid as the sole isolable product. Benesch, L.; Bury, P.; Houldsworth, S.J., Guillaneux, D.; Snieckus, V. unpublished results.
28. 2 directors appears not to be effective.
29. 2 directors appears not to be effective.
30. 2 directors appears not to be effective.
31. 2 directors appears not to be effective.
32. 2 directors appears not to be effective.
33. (12) All new compounds show analytical and spectral data consistent with the given structures.