Total synthesis of dolabelide C: A phosphate-mediated approach

Journal of Organic Chemistry

Volumn 76, Issue 11, 2011, Pages 4358-4370

  Hanson, Paul R ^a   Chegondi, Rambabu ^a   Nguyen, John ^a   Thomas, Christopher D ^a   Waetzig, Joshua D ^a   Whitehead, Alan ^a  

^a UNIVERSITY OF KANSAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BUILDING BLOCKES; CROSS METATHESIS; CYTOTOXIC; MACRO-CYCLIZATION; MACROLACTONES; MACROLIDES; OLEFIN REDUCTION; REGIO-SELECTIVE; TOTAL SYNTHESIS;

OLEFINS;

ALKENE; DOLABELIDE C; LACTONE; MACROLIDE; PHOSPHATE; UNCLASSIFIED DRUG;

ARTICLE; CYCLIZATION; DEPROTECTION REACTION; DRUG SYNTHESIS; HYDROGENATION; IONIZATION; ISOMERIZATION; OXIDATIVE COUPLING;

CATALYSIS; CYCLIZATION; MACROLIDES; PHOSPHATES; STEREOISOMERISM;

EID: 79957848869     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo2003506     Document Type: Article

References (63)

1. Ojika, M.; Nagoya, T.; Yamada, K. Tetrahedron Lett. 1995, 36, 7491-7494
2. Suenaga, K.; Nagoya, T.; Shibata, T.; Kigoshi, H.; Yamada, K. J. Nat. Prod. 1997, 60, 155-157
3. Grimaud, L.; Rotulo, D.; Ros-Perez, R.; Guitry-Azam, L.; Prunet, J. Tetrahedron Lett. 2002, 43, 7477-7479
4. Grimnaud, L.; de Mesmay, R.; Prunet, J. Org. Lett. 2002, 4, 419-421
5. Desroy, N.; Le Roux, R.; Phansavath, P.; Chiummiento, L.; Bonini, C.; Genêt, J.-P. Tetrahedron Lett. 2003, 44, 1763-1766
6. Schmidt, D. R.; Park, P. K.; Leighton, J. L. Org. Lett. 2003, 5, 3535-3537
7. Le Roux, R.; Desroy, N.; Phansavath, P.; Genêt, J.-P. Synlett 2005, 429-432
8. Keck, G. E.; McLaws, M. D. Tetrahedron Lett. 2005, 46, 4911-4914
9. Vincent, A.; Prunet, J. Synlett 2006, 2269-2271
10. Roche, C.; Desroy, N.; Haddad, M.; Phansavath, P.; Genêt, J.-P. Org. Lett. 2008, 10, 3911-3914
11. Park, P. K.; OMalley, S. J.; Schmidt, J. D. R.; Leighton, L. J. Am. Chem. Soc. 2006, 128, 2796-2797
12. Both antipodes of the bicyclic phosphate 5 and diol 7 have been previously constructed, see: Whitehead, A.; McReynolds, M. D.; Moore, J. D.; Hanson, P. R. Org. Lett. 2005, 7, 3375-3378 Recently, a four-step synthesis from commercially available 2,4-pentanedione (see ref 5a) has been developed to bicyclic phosphate 5; see: Venukadasula, P. K. M.; Chegondi, R.; Maitra, S.; Hanson, P. R. Org. Lett. 2010, 12, 1556-1559 For additional routes to 1,3-antidiols, see: Bode, S. E.; Wolberg, M.; Müller, M. Synthesis 2006, 557-588
13. Burke, S. D.; Muller, N.; Beaudry, C. M. Org. Lett. 1999, 1, 1827-1829
14. Burke, S. D.; Voight, E. A. Org. Lett. 2001, 3, 237-240
15. 2-symmetric diol using the Prins cyclization, see: Rychnovsky, S. D.; Yang, G.; Hu, Y.; Khire, U. R. J. Org. Chem. 1997, 62, 3022-3023
16. Rychnovsky, S. D.; Griesgraber, G.; Powers, J. P. Org. Synth. 1999, 77, 1-11
17. Mislow, K.; Siegel, J. J. Am. Chem. Soc. 1984, 106, 3319-3328
18. Eliel, E. L. Stereochemistry of Carbon Compounds; McGraw-Hill: New York, 1962.
19. 2Ru-CHPh (cat- A) (10) was shown to be not as effective in this desymmetrization reaction as cat- B. (11)
20. 2Ru-CHPh (cat- A): Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110
21. Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. 1995, 34, 2039-2041
22. 2Ru-CHPh (cat- B): Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953-956
23. Grubbs and co-workers have categorized various olefins by their relative rates of homodimerization correlating with the catalyst being used for CM. These types range from type I olefins, classified by rapid, reversible, homodimerization, to type IV olefins, which are spectators to CM. Varying product ratios can be observed when pairing different olefin types; mixing type I olefins yields a statistical mixture of CM and homodimerization, whereas CM between type I and type II olefin pairs is very selective and high yielding of CM products. Using differential reactivity of olefins allows one to design selective CM by properly pairing olefin partners. Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360-11370
24. Waetzig, J. D.; Hanson, P. R. Org. Lett. 2006, 8, 1673-1676
25. Waetzig, J. D.; Hanson, P. R. Org. Lett. 2008, 10, 109-112
26. Cat- C: Hoveyda-Grubbs second-generation catalyst: Garber, S. B; Kingsbury, J. S.; Gray, B. L; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168-8179
27. Meyers, A. G.; Zheng, B.; Movassaghi, M. J. Org. Chem. 1997, 62, 7507
28. For recent use of NBSH as a diimide source, see: Haukaas, M. H.; ODoherty, G. A. Org. Lett. 2002, 4, 1771-1774
29. Buszek, K. R.; Brown, N. J. Org. Chem. 2007, 72, 3125-3128
30. For a flavin-catalyzed generation of diimide, see: Imada, Y.; Iida, H.; Naota, T. J. Am. Chem. Soc. 2005, 127, 14544-14545
31. 2-symmetric monocyclic triene phosphate (ent-9).
32. For a related study on using Pd-formate reductions to form terminal olefins, see: Hughes, G.; Lautens, M.; Wen, C. Org. Lett. 2000, 2, 107-110
33. Chau, A.; Paquin, J.-F.; Lautens, M. J. Org. Chem. 2006, 71, 1924-1933
34. Helmboldt, H.; Koehler, D.; Hiersemann, M. Org. Lett. 2006, 8, 1573-1576
35. Umezawa, T.; Hayashi, T.; Sakai, H.; Teramoto, H.; Yoshikawa, T.; Izumida, M.; Tamatani, Y.; Hirose, T.; Ohfune, Y.; Shinada, T. Org. Lett. 2006, 8, 4971-4974
36. Chen, K.-M.; Hardtmann, G. E.; Prasad, K.; Repic, O.; Shapiro, M. J. Tetrahedron Lett. 1987, 28, 155-158
37. Evans, D. A.; Chapman, K. T.; Carreira, E. M. J. Am. Chem. Soc. 1998, 110, 3560-3578
38. Whitehead, A.; Waetzig, J. D.; Thomas, C. D.; Hanson, P. R. Org. Lett. 2008, 10, 1421-1424
39. Lucas, B. S.; Luther, L. M.; Burke, S. D. Org. Lett. 2004, 6, 2965-2968
40. Marshall, J. A.; Eidam, P. Org. Lett. 2004, 6, 445-448
41. Compound 11 was also synthesized through a one-pot protocol in 59% yield utilizing the same reagents shown in Scheme 3.
42. 4, LiI) generated a 1:1.5 mixture of diastereomers; see: Mori, Y.; Kuhara, M.; Takeuchi, A.; Suzuki, M. Tetrahedron Lett. 1988, 29, 5419-5422
43. Ghosh, A. K.; Lei, H. J. Org. Chem. 2002, 67, 8783-8788
44. Other reductants such as L-Selectride (dr = 1.7:1) and the CBS (Corey, E. J.; Shibata, S.; Bakshi, R. K. J. Org. Chem. 1988, 53, 2861-2863) reduction (dr = 2.2:1) gave favorable ratios as well
45. Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989-1993
46. Kawanami, Y.; Dainobu, Y.; Inanaga, J.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc. Jpn. 1981, 54, 943-944
47. Integration of the peaks areas of each mixture component resulted in a 2.6:1 ratio of 1 /demethyleneated product and the ratio between the title compound to the constitutional isomer as >20:1. (17). It is assumed that the constitutional isomer results from further Ru-H isomerization of dolabelide C due to a comparison of retention times with the aforementioned C14/C15 Z -configured dolabelide C analog originally separated during normal-phase flash chromatography.
48. Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 123-126
49. Overman, L. E.; Joe, D. Tetrahedron Lett. 1997, 38, 8635-8638 For references citing difficulty in constructing trisubstituted E-olefins using RCM, see: Hoye, T. R.; Zhao, H. Org. Lett. 1999, 1, 169-171
50. Smith, A. B.; Mesaros, E. F.; Meyer, E. A. J. Am. Chem. Soc. 2006, 128, 5292-5299
51. Jin, J.; Chen, Y.; Li, Y.; Wu, J.; Dai, W.-M. Org. Lett. 2007, 9, 2585-2588
52. Becker, J.; Bergander, K.; Frölich, R.; Hoppe, D. Angew. Chem., Int. Ed. 2008, 47, 1654-1657
53. The sequence was run simultaneously in two batches to obtain the quantities noted.
54. The olefin metathesis catalysts screened in Figure 2 were provided by Materia, Inc.
55. 2 and a conventional freeze/thaw technique.
56. The RCM was performed on 70 mg scale providing 14 mg of an analytically pure sample of the desired E -isomer and 10 mg of the Z -isomer.
57. Optical rotation was measured over several trials resulting in variation of both the value and sign of analytically pure 1 (determined by LC-MS analysis, see the Supporting Information). This phenomenon is consistent with hydrogen-bonding systems, where inconsistency is frequently observed. Abraham, E.; Davies, S. G.; Roberts, P. M.; Russell, A. J.; Thomson, J. E. Tetrahedron: Asymmetry 2008, 19, 1027-1047 and references cited within.
58. 13C NMR shifts of vinyl methyl and vinyl methylene carbon atoms associated with isolated trisubstituted double bonds are critically dependent on the configuration of the double bond as a result of the well-known γ-effect." For example
59. Purification of each isomer was achieved using two to three consecutive runs on normal-phase flash chromatography (see the Supporting Information).
60. Spectrum integrated to 41 total H, where the unassigned H was presumed to be an O-H peak undergoing H-D exchange.
61. Spectrum integrated to 71 total H, where the unassigned H was presumed to be an O-H peak undergoing H-D exchange. Only the O-H peaks did not match exactly to the reported data.
62. Spectrum integrated to 71 total H, where the unassigned H was presumed to be an O-H peak undergoing H-D exchange.
63. Spectrum integrated to 69 total H, where the unassigned Hs were presumed to be O-H peaks undergoing H-D exchange.