Enantioselective synthesis of the C-14 to C-5 cyclopentane segment of jatrophane diterpenes

Tetrahedron Letters

Volumn 45, Issue 2, 2004, Pages 289-292

  Helmboldt, Hannes ^a   Rehbein, Julia ^a   Hiersemann, Martin ^a  

^a DRESDEN UNIVERSITY OF TECHNOLOGY   (Germany)

Author keywords

Carbonyl ene reaction; Diterpene; Euphorbia; Jatrophane; Total synthesis

Indexed keywords

ANTINEOPLASTIC AGENT; DITERPENE;

ALDOL REACTION; ARTICLE; CHEMICAL REACTION; CHROMATOGRAPHY; CIS TRANS ISOMERISM; DIASTEREOISOMER; DRUG SYNTHESIS; ENANTIOMER; ENANTIOSELECTIVITY; HORNER WADSWORTH EMMONS REACTION; MITSUNOBU REACTION; OXIDATION REDUCTION REACTION; REACTION ANALYSIS; THERMODYNAMICS;

EUPHORBIA;

EID: 0346366648     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2003.10.171     Document Type: Article

References (36)

1. Valente C., Ferreira M.J.U., Abreu P.M., Pedro M., Cerqueira F., Nascimento M.S.J. Planta Medica. 69:2003;361-366.
2. Miglietta A., Gabriel L., Appendino G., Bocca C. Cancer Chemother. Pharmacol. 51:2003;67-74.
3. Corea G., Fattorusso E., Lanzotti V., Taglialatela-Scafati O., Appendino G., Ballero M., Simon P.-N., Dumontet C., Di Pietro A. J. Med. Chem. 46:2003;3395-3402.
4. (a) Aylward, J. H.; Parsons, P. G. Int. Pat. WO 02/11743 A2 (A3), 2002; Chem. Abstr. 2002, 136, 177959x
5. (b) Aylward, J. H.; Parsons, P. G.; Suhrbier, A.; Turner, K. A. Int. Pat. WO 01/93885 A1, 2001; Chem. Abstr. 2002, 136, 31680c
6. (c) Aylward, J. H.; Parsons, P. G.; Suhrbier, A.; Turner, K. A. WO 01/93884 A1, 2001; Chem. Abstr. 2002, 136, 42795v
7. (d) Aylward, J. H.; Parsons, P. G.; Suhrbier, A.; Turner, K. A. WO 01/93883 A1, 2001; Chem. Abstr. 2002, 136, 31656z
8. (e) Aylward, J. H. WO 99/08994 A1, 1999; Chem. Abstr. 1999, 130, 205113p.
9. (a). Studies concerning the intramolecular carbonyl ene reaction of α-keto esters are scarce. For examples under thermal conditions, see: Hiersemann M. Eur. J. Org. Chem. 2001;483-491
10. (b) Hiersemann M. Synlett. 2000;415-417
11. c). For catalytic asymmetric procedures, see: Kaden S., Hiersemann M. Synlett. 2002;1999-2002 Yang D., Yang M., Zhu N. Org. Lett. 5:2003;3749-3752.
12. (c). For catalytic asymmetric procedures, see: Kaden S., Hiersemann M. Synlett. 2002;1999-2002 Yang D., Yang M., Zhu N. Org. Lett. 5:2003;3749-3752.
13. (a) Evans D.A., Nelson J.V., Vogel E., Taber T.R. J. Am. Chem. Soc. 103:1981;3099-3111
14. (b) Evans D.A., Bartroli J., Shih T.L. J. Am. Chem. Soc. 103:1981;2127-2129.
15. (a) The aldol addition was realized as described in Smith A.B., Minbiole K.P., Verhoest P.R., Schelhaas M. J. Am. Chem. Soc. 123:2001;10942-10953
16. (b) . the auxiliary was removed as described in Sunazuka T., Hirose T., Shirahata T., Harigaya Y., Hayashi M., Komiyama K., Omura S., Smith A.B. J. Am. Chem. Soc. 122:2000;2122-2123.
17. Parikh-Doering oxidation, see: Parikh J.R., Doering W.v.E. J. Am. Chem. Soc. 89:1967;5505-5507.
18. (a) The phosphonates 11a,b were synthesized according to Horne D., Gaudino J., Thompson W.J. Tetrahedron Lett. 25:1984;3529-3532
19. (b) The HWE reaction was realized according to Ouellet L., Langlois P., Deslongchamps P. Synlett. 1997;689-699
20. (c) further examples for the construction of an enol ether double bond by a HWE reaction, see: Grell W., Machleidt H. Liebigs Ann. Chem. 699:1966;53-59
21. (d) Ireland R.E., Mueller R.H., Willard A.K. J. Am. Chem. Soc. 98:1976;2868-2877
22. (e) Ireland R.E., Mueller R.H., Willard A.K. J. Org. Chem. 41:1976;986-996
23. Nakamura E. Tetrahedron Lett. 22:1981;663-666
24. (g) Overman L.E., Rogers B.N., Tellew J.E., Trenkle W.C. J. Am. Chem. Soc. 119:1997;7159-7160
25. (h) Paterson I., McLeod M.D. Tetrahedron Lett. 38:1997;4183-4186
26. (i) Bélanger G., Hong F., Overman L.E., Rogers B.N., Tellew J.E., Trenkle W.C. J. Org. Chem. 67:2002;7880-7883.
27. Assignment of the double bond configuration based on the chemical shift of the vinyl ether double bond proton, see: Hiersemann M. Synthesis. 2000;1279-1290. and Ref. [9f].
28. 3).
29. An increased reaction temperature or a prolonged reaction time led to inferior chemical yields.
30. 5d did not afford the desired product 5d.
31. The configurational assignment is based on extensive NOESY experiments.
32. 1 at C-3 is directed toward the concave face of the bicyclo[4.3.0]nonane-like transition state (Fig. 3).
33. 4Si: C, 63.11; H, 10.00. Found: C, 62. 95; H, 10.21.
34. The thermal intramolecular carbonyl ene reaction of 6c has been realized on a 4 mmol scale. Up-scaling has no detrimental effect on the yield or the diastereoselectivity.
35. Mitsunobu O. Synthesis. 1981;1-28.
36. 3).