Transition metal-diene complexes in organic synthesis, part 24 9b total synthesis of the naturally occurring free radical scavenger carazostatin

Synlett

Volumn 1995, Issue 9, 1995, Pages 981-983

  Knölker, Hans Joachim ^a   Hopfmann, Thomas ^a  

^a UNIVERSITY OF KARLSRUHE   (Germany)

Author keywords

carazostatin; carbazole alkaloids; free radical scavenger; quinone imine cyclization; tricarbonyliron diene complexes

Indexed keywords

EID: 84862288286     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-1995-5121     Document Type: Article

References (31)

1. W. Palinski, M. E. Rosenfeld, S. Yla-Herttuala, G. C. Gurtner, S. S. Socher, S. W. Butler, S. Parthasarathy, T. E. Carew, D. Steinberg, J. L. Witztum, Proc. Natl. Acad. Sci. U.S.A. 1989, 86, 1372.
2. R. Bolli, M. O. Jeroudi, B. S. Patel, C. M. DuBose, E. K. Lai, R. Roberts, P. B. McCay, Proc. Natl. Acad. Sci. U.S.A. 1989, 86, 4695.
3. K. Shin-ya, K. Furihata, Y. Hayakawa, H. Seto, Y. Kato, J. Clardy, Tetrahedron Lett. 1991, 32, 943.
4. D. W. Brown, P. R. Graupner, M. Sainsbury, H. G. Shertzer, Tetrahedron 1991, 47, 4383.
5. K. Shin-ya, K. Furihata, Y. Teshima, Y. Hayakawa, H. Seto, Tetrahedron Lett. 1992, 33, 7025; et loc. cit.
6. P. A. Cerutti, Science 1985, 227, 375.
7. S. Kato, H. Kawai, T. Kawasaki, Y. Toda, T. Urata, Y. Hayakawa, Antibiotics 1989, 42, 1879.
8. M. Iwatsuki, E. Niki, S. Kato, K. Nishikori, Chem. Lett. 1992, 1735.
9. For previous total syntheses, see
10. P. M. Jackson, C. J. Moody, Synlett 1990, 521.
11. K. Shin, K. Ogasawara, Chem. Lett. 1995, 289.
12. U. Pindur, Chimia 1990, 44, 406.
13. J. Bergman, B. Pelcman, Pure Appl. Chem. 1990, 62, 1967.
14. H-J. Knolker In Organic Synthesis via Organometallics; K. H. Dotz, R. W. Hoffmann, Eds.; Vieweg: Braunschweig, 1991; p. 119.
15. H-J. Knolker, Synlett 1992, 371.
16. C. J. Moody, Synlett 1994, 681.
17. For a review on transition metal-mediated synthesis of carbazole derivatives, see: H-J. Knolker In Advances in Nitrogen Heterocycles, Vol. 1; C. J. Moody, Ed.; JAI Press: Greenwich, CT (USA), 1995; p. 173.
18. H-J. Knolker, M. Bauermeister, D. Blaser, R. Boese, J-B. Pannek, Angew. Chem. 1989, 101, 225
19. Angew. Chem. Int. Ed. Engl. 1989, 28, 223. H-J. Knolker, M. Bauermeister, J-B. Pannek, D. Blaser, R. Boese, Tetrahedron 1993, 49, 841.
20. H-J. Knolker, M. Bauermeister, Helv. Chim. Acta 1993, 76, 2500. Part 23
21. H-J. Knolker, E. Baum, T. Hopfmann, Tetrahedron Lett. 1995, 36, in print.
22. H-J. Knolker, M. Bauermeister, J-B. Pannek, M. Wolpert, Synthesis 1995, 397.
23. Methyl 2-decynoate 4 was prepared by adaptation of literature procedures (L. Brandsma, Preparative Acetylenic Chemistry, second edition; Elsevier: Amsterdam, 1988): 1.1 eq n-BuLi were added to a solution of 1-nonyne in diethyl ether at-30C. To this solution 1.4 eq methyl chloroformate were added and the reaction mixture was allowed to warm up to r. t. Workup (hydrolysis with water, extraction with ether, drying of the organic layer over MgSC4, and removal of the solvent) afforded 4 in 94% yield, which was used as crude product.
24. C. C. Kanakam, N. S. Mani, H. Ramanathan, G. S. R. Subba Rao, J. Chem. Soc. Perkin Trans. 1 1989, 1907.
25. The regio-and stereoselectivity of this reaction is in agreement with analogous cases previously investigated, see for example: H-J. Knolker, M. Bauermeister, J-B. Pannek, Chem. Ber. 1992, 125, 2783.
26. H-J. Knolker, J. Prakt. Chem. 1995, 337, 75.
27. Manganese dioxide (precipitated active, art. 805958) from Merck-Schuchardt.
28. C-NMR spectra and results of the DEPT experiments (100 MHz, CDCI3) of the quinone imines. 9 (anti-imine stereoisomer): 5 = 11.99 (CH3), 14.10 (CH3), 22.63 (CH2), 27.45 (CH2), 29.03 (CH2), 29.06 (CH2), 29.86 (CH2), 31.72 (CH2), 32.77 (CH2), 37.25 (CH), 60.46 (CH), 62.95 (CH), 84.86 (CH), 86.18 (CH), 127.09 (CH), 135.67 (C), 141.43 (C), 157.27 (C), 165.31 (C=N), 187.67 (C=0), 211.66 (3 CO). 10: S= 11.98 (CH3), 14.07 (CH3), 22.60 (CH2), 27.83 (CH2), 29.12 (CH2), 29.16 (CH2), 29.74 (CH2), 31.78 (CH2), 45.01 (CH), 57.24 (CH), 59.13 (CH), 78.08 (CH), 85.10 (CH), 86.26 (CH), 122.29 (CH), 138.30 (C), 142.69 (C), 155.44 (C), 163.36 (C=N), 187.65 (C=0), 210.41 (3 CO).
29. J. Fatiadi, Synthesis 1976, 65.
30. Y. Shvo, E. Hazum, Chem. Soc. Chem. Commun. 1974, 336.
31. Carazostatin: colorless crystals, m.p. 153-155C (lit.4 m.p. 149-152C, lit.6a m.p. 162-163C, lit.6b m.p. 159.5-160.5C). UV (MeOH): X = 217, 233, 253, 264, 295 (sh), 302, 341, 350 nm. 13C-NMR (100 MHz, CDC13): 8 = 11.98 (CH3), 14.12 (CH3), 22.68 (CH2), 28.78 (CH2), 29.32 (CH2), 29.53 (CH2), 30.00 (CH2), 31.86 (CH2), 102.96 (CH), 110.62 (CH), 118.89 (CH), 120.06 (CH), 120.79 (C), 121.37 (C), 123.66 (C), 124.12 (C), 125.24 (CH), 133.97 (C), 139.75 (C), 148.09 (C).