Probing competitive pathways in building a hydroazulene moiety by reductive cyclization

Tetrahedron Letters

Volumn 45, Issue 19, 2004, Pages 3827-3829

  Mandal, Mihirbaran ^a   Danishefsky, Samuel J ^a,b  

^a MEMORIAL SLOAN KETTERING CANCER CENTER   (United States)

^b Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AZULENE DERIVATIVE; DEUTERIUM; IODINE DERIVATIVE; VINYL DERIVATIVE;

ARTICLE; CYCLIZATION; MOLECULAR PROBE; OXIDATION; REDUCTION; STEREOCHEMISTRY; SYNTHESIS;

EID: 1842861654     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2004.02.161     Document Type: Article

References (45)

1. Total synthesis: Dudley G.B., Danishefsky S.J. Org. Lett. 3:2001;2399-2402.
2. Dudley G.B., Tan D.S., Kim G., Tanski J.M., Danishefsky S.J. Tetrahedron Lett. 42:2001;6789-6791.
3. Dudley G.B., Danishefsky S.J., Sukenick G. Tetrahedron Lett. 43:2002;5605-5606.
4. Lin S., Dudley G.B., Tan D.S., Danishefsky S.J. Angew. Chem., Int. Ed. 41:2002;2188-2191.
5. Tan D.S., Dudley G.B., Danishefsky S.J. Angew. Chem., Int. Ed. 41:2002;2185-2188.
6. Shi B., Hawryluk N.A., Snider B.B. J. Org. Chem. 68:2003;1030-1042.
7. For recent synthetic studies inspired by guanacastepene cf. inter alia: Brummond K.M., Gao D. Org. Lett. 5:2003;3491-3494.
8. Boyer F.-D., Hanna I. Tetrahedron Lett. 43:2002;7469-7472.
9. Du X., Chu H.V., Kwon O. Org. Lett. 5:2003;1923-1926.
10. Magnus P., Waring M.J., Ollivier C., Lynch V. Tetrahedron Lett. 42:2001;4947-4950.
11. Magnus P., Ollivier C. Tetrahedron Lett. 43:2002;9605-9609.
12. Mehta G., Umarye J.D., Gagliardini V. Tetrahedron Lett. 43:2002;6975-6978.
13. Mehta G., Umarye J.D. Org. Lett. 4:2002;1063-1066.
14. Mehta G., Umarye J.D., Srinivas K. Tetrahedron Lett. 44:2003;4233-4237.
15. Nakazaki A., Sharma U., Tius M.A. Org. Lett. 4:2002;3363-3366.
16. Nguyen T.M., Seifert R.J., Mowrey D.R., Lee D. Org. Lett. 4:2002;3959-3962.
17. Nguyen T.M., Lee D. Tetrahedron Lett. 43:2002;4033-4036.
18. Shipe W.D., Sorensen E.J. Org. Lett. 4:2002;2063-2066.
19. Snider B.B., Shi B. Tetrahedron Lett. 42:2001;9123-9126.
20. Snider B.B., Hawryluk N.A. Org. Lett. 3:2001;569-572.
21. Hughes C.C., Kennedy-Smith J.J., Trauner D. Org. Lett. 5:2003;4113-4115.
22. Isolation: Brady S.F., Singh M.P., Janso J.E., Clardy J. J. Am. Chem. Soc. 122:2000;2116-2117.
23. Brady S.F., Bondi S.M., Clardy J. J. Am. Chem. Soc. 123:2001;9900-9901.
24. Singh M.P., Janso J.E., Luckman S.W., Brady S.F., Clardy J., Greenstein M., Maiese W.M. J. Antibiot. 53:2000;256-261.
25. Büchi G., Egger B. J. Org. Chem. 36:1971;2021-2023.
26. Dauben W.G., Michno D.M. J. Org. Chem. 42:1977;682-685.
27. Corey E.J., Kuwajima I. J. Am. Chem. Soc. 92:1970;395-396.
28. Piers E., Walker S.D., Armbrust R. J. Chem. Soc., Perkin Trans. 1. 2000;633-637.
29. Neumann H., Seebach D. Tetrahedron Lett. 1976;4839-4842.
30. In our analysis we deliberately avoided dealing with the interesting question as to whether cyclization involves a mature vinyllithium species, or radical anionoid species en route to the fully formed vinyllithium entity, cf. inter alia: Curran D.P., Gu X., Zhang W., Dowd P. Tetrahedron. 53:1997;9023-9042.
31. An early example of the use of reductive cyclization occurs in the context of our total synthesis of patchouli and epi-patchouli alcohol: Danishefsky S.J., Dumas D. Chem. Commun. 1968;1287-1288.
32. For more recent work in this area cf. inter alia: Piers E., Renaud J., Rettig S.J. Synthesis. 1998;590-602.
33. Piers E., Cook K.L., Rogers C. Tetrahedron Lett. 35:1994;8573-8576.
34. Mori M., Isono N., Kaneta N., Shibasaki M. J. Org. Chem. 58:1993;2972-2976.
35. Piers E., Renaud J. J. Org. Chem. 58:1993;11-13.
36. Mori M., Kaneta N., Isono N., Shibasaki M. Tetrahedron Lett. 32:1991;6139-6142.
37. Mori M., Watanabe N., Kaneta N., Shibasaki M. Chem. Lett. 1991;1615-1618.
38. Piers E., Boulet S.L. Synlett. 1998;516-518.
39. Cooke M.P. Jr., Widener R.K. J. Org. Chem. 52:1987;1381-1396.
40. Piers E., Harrison C.L., Zetina-Roche C. Org. Lett. 3:2001;3245-3247.
41. cf. Piers E., Renaud J., Retting S.J. Synthesis. 1998;590.
42. Mass spectral analysis failed to show a peak for a mono deutero or non deutero version of 9, although the minimum detection limits of protio analogs have not been established (see implications in Ref. 12).
43. The incorporation of deuterium into the vinylic position with retention of the Z configuration was ascertained from proton NMR analysis. Also see Ref. 7 for the configurational stability of vinyllithium species.
44. cf. Seebach D., Neumann H. Chem. Ber. 107:1974;847-853. The only alternative explanation would invoke an extraordinarily large isotope effect from residual protio compound in 9.
45. Since dideuterated compound 9 afforded 11 and 13 during reductive cyclization, the possibility that the primary source of reduction product arises solely from intermolecular proton tranfer to 4 via either 3 or another molecule of 4 is excluded. Our data do not exclude the possibility that the small amount of proton transfer to the vinyllithium (presumably from the butyl iodide) arises in a molecule containing an enolate, which is incapable of cyclization. The enolate would have been formed by direct deprotonation of the ketone by n-BuLi.