Concise stereoselective synthesis of (-)-podophyllotoxin by an intermolecular iron(III)-catalyzed Friedel-Crafts alkylation

Angewandte Chemie - International Edition

Volumn 47, Issue 39, 2008, Pages 7557-7559

  Stadler, Daniel ^a   Bach, Thorsten ^a  

^a TECHNICAL UNIVERSITY OF MUNICH   (Germany)

Author keywords

Antitumor agents; Catalysis; Diastereoselectivity; Natural products; Total synthesis

Indexed keywords

ALKYLATION; CHEMICAL BONDS; HYDROCARBONS; IRON COMPOUNDS; RAW MATERIALS; STEREOCHEMISTRY; STEREOSELECTIVITY; SYNTHESIS (CHEMICAL);

ANTITUMOR AGENTS; CATALYSIS; DIASTEREOSELECTIVITY; NATURAL PRODUCTS; TOTAL SYNTHESIS;

CHEMICAL REACTIONS;

IRON; PODOPHYLLOTOXIN;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; CYCLIZATION; STEREOISOMERISM; SYNTHESIS;

ALKYLATION; CATALYSIS; CYCLIZATION; IRON; MOLECULAR STRUCTURE; PODOPHYLLOTOXIN; STEREOISOMERISM;

EID: 54749151723     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200802611     Document Type: Article

References (38)

1. M. Gordaliza, P. A. García, J. M. Miguel del Corral, M. A. Castro, M. A. Gómez-Zurita, Toxicon 2004, 44, 441-459.
2. For reviews, see: a) R. S. Ward, Phytochem. Rev. 2003, 2, 391-400;
3. b) R. S. Ward, Nat. Prod. Rep. 1999, 16, 75-96;
4. c) R. S. Ward, Synthesis 1992, 719-730;
5. d) R. S. Ward, Tetrahedron 1990, 46, 5029-5041.
6. R. C. Andrews, S. J. Teague, A. I. Meyers, J. Am. Chem. Soc. 1988, 110, 7854-7858.
7. For the synthesis of enantiomerically pure (+)-or (-)-podophyllotoxin, see: a) R. Van Speybroeck, H. Guo, J. van der Eycken, M. Vandewalle, Tetrahedron 1991, 47, 4675-4682;
8. b) E. J. Bush, D. W. Jones, J. Chem. Soc. Chem. Commun. 1993, 1200-1201;
9. E. J. Bush, D. W. Jones, J. Chem. Soc. Perkin Trans. 1 1996, 151-155;
10. c) S. B. Hadimani, R. P. Tanpure, S. V. Bhat, Tetrahedron Lett. 1996, 37, 4791-4794;
11. d) D. B. Berkowitz, S. Choi, J.-H. Maeng, J. Org. Chem. 2000, 65, 847-860;
12. e) A. J. Reynolds, A. J. Scott, C. I. Turner, M. S. Sherburn, J. Am. Chem. Soc. 2003, 125, 12108-12109.
13. For the synthesis of (-)-epipodophyllotoxin, see: U. Engelhardt, A. Sarkar, T. Linker, Angew. Chem. 2003, 115, 2591-2593;
14. Angew. Chem. Int. Ed. 2003, 42, 2487-2489, and references therein.
15. During our study, a formal total synthesis of (±)-podophyllotoxin was reported in which a Heck reaction was used for an intramolecular arylation: F. Mingoia, M. Vitale, D. Madec, G. Prestat, G. Poli, Tetrahedron Lett. 2008, 49, 760-763.
16. a) K. Kondo, F. Mori, Chem. Lett. 1974, 741-742;
17. b) F. Ishibashi, E. Taniguchi, Bull. Chem. Soc. Jpn. 1988, 61, 4361-4366.
18. C. Gnamm, S. Förster, N. Miller, K. Brödner, G. Helmchen, Synlett 2007, 790-794.
19. a) D. Stadler, T. Bach, Chem. Asian J. 2008, 3, 272-284;
20. b) D. Stadler, F. Mühlthau, P. Rubenbauer, E. Herdtweck, T. Bach, Synlett 2006, 2573-2576;
21. c) F. Mühlthau, D. Stadler, A. Goeppert, G. A. Olah, G. K. S. Prakash, T. Bach, J. Am. Chem. Soc. 2006, 128, 9668-9675.
22. P. Rubenbauer, T. Bach, Tetrahedron Lett. 2008, 49, 1305-1309.
23. For recent reviews on iron catalysis, see: a) C. Bolm, J. Legros, J. Le Paih, L. Zani, Chem. Rev. 2004, 104, 6217-6254;
24. b) S. Enthaler, K. Junge, M. Beller, Angew. Chem. 2008, 120, 3363-3367;
25. Angew. Chem. Int. Ed. 2008, 47, 3317-3321.
26. P. Rubenbauer, T. Bach, Adv. Synth. Catal. 2008, 350, 1125-1130.
27. Besides the thermodynamic preference for the formation of isomer 8 with a pseudoequatorial aryl group at C1, the higher nucleophilicity of the trimethoxyphenyl group may favor attack at the activated aldehyde carbon atom.
28. a) H. A. Dieck, R. F. Heck, J. Am. Chem. Soc. 1974, 96, 1133-1136;
29. b) R. F. Heck, Org. React. 1982, 27, 345-390;
30. c) I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009-3066;
31. d) K. Olofsson, H. Sahlin, M. Larhed, A. Hallberg, J. Org. Chem. 2001, 66, 544-549.
32. For the synthesis of (-)-4-deoxy-4-methylenepodophyllotoxin (9) from (-)-podophyllotoxin, see: E. Roulland, P. Magiatis, P. Arimondo, E. Bertounesque, C. Monneret, Bioorg. Med. Chem. 2002, 10, 3463-3471.
33. a) Y. Okude, S. Hirano, T. Hiyama, H. Nozaki, J. Am. Chem. Soc. 1977, 99, 3179-3181;
34. b) T. Hiyama, K. Kimura, H. Nozaki, Tetrahedron Lett. 1981, 22, 1037-1040;
35. c) G. C. Hargaden, P. J. Guiry, Adv. Synth. Catal. 2007, 349, 2407-2424;
36. d) R. L. Halterman, C. Zhu, Tetrahedron Lett. 1999, 40, 7445-7448.
37. For the synthesis of (-)-podophyllotoxon from (-)-podophyllotoxin, see: P. H. Höfert, R. Matusch, Helv. Chim. Acta 1994, 77, 771-777.
38. H. Yamaguchi, M. Arimoto, S. Nakajima, M. Tanoguchi, Y. Funaka, Chem. Pharm. Bull. 1986, 34, 2056-2060.