Biomimetic explorations towards the bisorbicillinoids: Total synthesis of bisorbicillinol, bisorbibutenolide, and trichodimerol

Angewandte Chemie - International Edition

Volumn 38, Issue 23, 1999, Pages 3555-3559

  Nicolaou, K C ^a,b   Simonsen, Klaus B ^a,b   Vassilikogiannakis, Georgios ^a,b   Baran, Phil S ^a,b   Vidali, Veroniki P ^c   Pitsinos, Emmanuel N ^c   Couladouros, Elias A ^c,d  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

^c NCSR DEMOKRITOS   (Greece)

^d AGRICULTURAL UNIVERSITY OF ATHENS   (Greece)

Author keywords

Biomimetic synthesis; Bisorbicillinols; Dimerizations; Natural products; Trichodimerol

Indexed keywords

BISORBIBUTENOLIDE; BISORBICILLINOID DERIVATIVE; BISORBICILLINOL; NATURAL PRODUCT; TRICHODIMEROL; TUMOR NECROSIS FACTOR ALPHA; UNCLASSIFIED DRUG;

ANTIOXIDANT ACTIVITY; ARTICLE; DIMERIZATION; DRUG ACTIVITY; DRUG STRUCTURE; DRUG SYNTHESIS; FUNGUS; OXIDATION; SEPTIC SHOCK;

EID: 0033521220     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19991203)38:23<3555::AID-ANIE3555>3.0.CO;2-Z     Document Type: Article

References (24)

1. The term "bisorbicillinoids" was recently introduced by us to describe all dimeric natural products derived from sorbicillin: K. C. Nicolaou, R. Jautelat, G. Vassilikogiannakis, P. S. Baran, K. B. Simonsen, Chem. Eur. J. 1999, 5, 3651-3665.
2. N. Abe, T. Murata, A. Hirota, Biosci. Biotechnol. Biochem. 1998, 62, 661-66.
3. a) N. Abe, T. Murata, A. Hirota, Biosci. Biotechnol. Biochem. 1998, 62, 2120-2126;
4. b) a second fungal metabolite differing from bisorbibutenolide (2) only in its relative configuration at C9 was isolated in 1997 and named trichotetronine: O. Shirota, V. Pathak, C. F. Hossain, S. Sekita, K. Takatori, M. Satake, J. Chem. Soc. Perkin Trans. I 1997, 2961-2964.
5. a) R. Andrade, W. A. Ayer, P. P. Mehe, Can. J. Chem. 1992, 70, 2526-2535;
6. b) G. A. Warr, J. A. Veitch, A. W. Walsh, G. A. Hesler, D. M. Pirnik, J. E. Leet, P.-F. M. Lin, I. A. Medina, K. D. McBrien, S. Forenza, J. M. Clark, K. S. Lam, J. Antibiot. 1996, 49, 234-240.
7. a) L. S. Trifonov, H. Hilpert, P. Floersheim, A. S. Dreiding, D. M. Rast, R. Skrivanova, L. Hoesch, Tetrahedron 1986, 42, 3157-3179:
8. b) M. Kontani, Y. Sakagami, S. Marumo, Tetrahedron Lett. 1994, 35, 2577-2580.
9. a) D. J. Cram, M. Tishler, J. Am. Chem. Soc. 1948, 70, 4238-4239;
10. b) D. J. Cram, J. Am. Chem. Soc. 1948, 70, 4240-4243.
11. a) L. S. Trifonov, A. S. Dreiding, L. Hoesch, D. M. Rast, Helv. Chim. Acta 1981, 64, 1843-1846;
12. b) L. S. Trifonov, J. H. Bieri, R. Prewo, A. S. Dreiding, L. Hoesch, D. M. Rast, Tetrahedron 1983, 39, 4243-4256.
13. A previous proposal regarding the biosynthesis of bisvertinol (6) from sorbicillin postulates a different pathway, in which an initial epoxidation of sorbicillin followed by reduction and then dimerization and ketalization is believed to be involved.[7]
14. W. Baker, H. F. Bondy, J. F. W. McOmie, H. R. Tunnicliff, J. Chem. Soc. 1949, 2834-2835.
15. J. F. W. McOmie, M. S. Tute, J. Chem. Soc. 1958, 3226-3227. This method was found to be superior on larger scale to the procedure described by the Sartori group; see F. Bigi, G. Casiraghi, G. Casnati, S. Marchesi, G. Sartori, C. Vignali, Tetrahedron 1984, 40, 4081-4084.
16. J. F. W. McOmie, M. S. Tute, J. Chem. Soc. 1958, 3226-3227. This method was found to be superior on larger scale to the procedure described by the Sartori group; see F. Bigi, G. Casiraghi, G. Casnati, S. Marchesi, G. Sartori, C. Vignali, Tetrahedron 1984, 40, 4081-4084.
17. 13C NMR spectra of bisorbicillinol (1) and bisorbibutenolide (2).
18. The acetate 7a did not give any Diels-Alder product 1 when heated in benzene or in AcOH for several hours.
19. a) D. H. R. Barton, P.D. Magnus. M. N. Rosenfeld, J. Chem. Soc. Chem. Commun. 1975, 301-301;
20. b) D. H. R. Barton, P. D. Magnus, J. C. Quinney, J. Chem. Soc. Perkin Trans. I 1975, 1610-1614; see also: E. Adler, K. Holmberg, Acta. Chem. Scand. Ser. B 1974, 28, 465-472.
21. b) D. H. R. Barton, P. D. Magnus, J. C. Quinney, J. Chem. Soc. Perkin Trans. I 1975, 1610-1614; see also: E. Adler, K. Holmberg, Acta. Chem. Scand. Ser. B 1974, 28, 465-472.
22. Attempts to induce 7a to react under Lewis acid catalysis conditions were also made. Interestingly, when 7a was exposed to TBSOTf or TMSOTf, 3 was the major product formed together with small amounts of 1. TBS = tert-butyldimethylsilyl, Tf = trifluormethanesulfonyl, TMS = trimethylsilyl.
23. Trichodimerol (4) was unavailable to us for direct comparison.
24. For the first synthesis of enantiomerically pure trichodimerol by dimerization of resolved acetate 7a, see D. Barnes-Seeman, E. J. Corey, Org. Lett. 1999, 1, 1503-1504.