Parallel kinetic resolution approach to the cyathane and cyanthiwiginditerpenes using a cyclopropanation/cope rearrangement

Angewandte Chemie - International Edition

Volumn 48, Issue 13, 2009, Pages 2398-2402

  Miller, Laura C ^a   Ndungu, J Maina ^a   Sarpong, Richmond ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Diterpenes; Kinetic resolution; Natural products; Stereodivergent synthesis

Indexed keywords

RHODIUM;

CYCLOPROPANATION; DIASTEREOMERIC; DITERPENES; KINETIC RESOLUTION; NATURAL PRODUCTS; PARALLEL KINETIC RESOLUTION; RACEMIC MIXTURES; STEREODIVERGENT SYNTHESIS;

KINETICS;

CYANTHIWIGIN F; CYANTHIWIGIN U; CYATHANE; DITERPENE; RHODIUM;

CATALYSIS; CHEMISTRY; CYCLIZATION; KINETICS; STEREOISOMERISM; SYNTHESIS;

CATALYSIS; CYCLIZATION; DITERPENES; KINETICS; RHODIUM; STEREOISOMERISM;

EID: 70349783658     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200806154     Document Type: Article

References (47)

1. H. B. Kagan, J. C. Fiaud, Top. Stereochem. 1988, 18,249-330.
2. This scenario requires a selectivity factor, s (i.e. ke(R)kAe(.s))> tobee greater than 200. See Ref. [1].
3. For complications in simple kinetic resolutions arising fromconcentration effects and selectivity factors, see: J. Eames, Angew.Chem. 2000, 112, 913-916;
4. Angew. Chem. Int. Ed. 2000, 39, 885-888.
5. a) E. Vedejs, X. Chen, J. Am. Chem. Soc. 1997, 119,2584-2585;
6. b) J. R. Dehli, V. Gotor, Chem. Soc. Rev. 2002, 31,365-370.
7. For a definition of stereodivergent parallel kinetic resolution, see Ref.[4].
8. a) W. A. Ayer, H. Taube, Tetrahedron Lett. 1972, 13,1917-1920;
9. b) A. D. Allbutt, W. A. Ayer, H. J. Brodie, B. N. Johri, H. Taube,Can. J. Microbiol. 1971, 17, 1401-1407.
10. a) W. A. Ayer, S. P. Lee, Can. J. Chem. 1979, 57,3332-3337;
11. b) H. Kawagishi, A. Shimada, S. Hosokawa, H. Mori, H. Sakamoto, Y.Ishiguro, S. Sakemi, J. Bordner, N. Kojima, S. Funikawa, TetrahedronLett. 1996, 37, 7399-7402;
12. c) W. A. Ayer, T. Yoshida, D. M. J. van Schie, Can. J. Chem.1978, 56, 2113-2120;
13. d) D. Green, I. Goldberg, Z. Stein, M. Ilan, Y. Kashman, Nat. Prod.Lett. 1992, 1, 193-199;
14. e) J. Peng, K. Walsh, V. Weedman, J. D. Bergthold, J. Lynch, K. L. Lieu,I. A. Braude, M. Kelly, M.T. Hamann, Tetrahedron 2002, 58,7809-7819.
15. Y. Obara, H. Kobayashi, T. Ohta, Y. Ohizumi, N. Nakahata, Mol,Pharmacol. 2001, 59, 1287-1289.
16. Total syntheses include: a) B. B. Snider, N. H. Vo, S. V. O'Neil, B. M.Foxman, J. Am. Chem. Soc. 1996, 118, 7644-7645;
17. b) B. B. Snider, N.H. Vo, S. V. O'Neil, J. Org Chem. 1998,63, 4732-4740;
18. c) for additional references to previous syntheses, see the SupportingInformation.
19. For approaches to the cyathane core containing five-, six-, andseven-membered rings, see the Supporting Information.
20. For a synthesis of cyanthiwigin AC (which possesses a rearrangedskeleton) see: T. J. Reddy, G. Bordeau, L. Trimble, Org. Lett.2006, 8, 5585-5588.
21. a) M. W. B. Pfeiffer, A. J. Phillips, J. Am. Chem. Soc.2005, 127, 5334-5335;
22. b) M. W. B. Pfeiffer, A. J. Phillips, Tetrahedron Lett.2008, 49, 6860-6861.
23. J. Enquist, Jr., B. M. Stoltz, Nature 2008, 453,1228-1231.
24. Z. G. Hajos, D. R. Parrish, Organic Syntheses Collect. Vol. VII,Wiley, New York, 1990, pp. 363-368.
25. For a review, see: T. Hudlicky, R. Fan, J. W. Reed, K. G. Gadamasetti,Org. React. 1992, 41, 1-133.
26. Only a single enantiomer is depicted for clarity.
27. O. Lepage, C. Stone, P. Deslongchamps, Org. Lett. 2002,4, 1091-1094.
28. G. M. Rubottom, M. A. Vazquez, D. R. Pelegrina, Tetrahedron Lett.1974, 15, 4319-4322.
29. a) E. J. Corey, T. M. Eckrich, Tetrahedron Lett. 1984,25, 2415-2418;
30. b) G. S. Sheppard etal., J. Med. Chem. 2006, 49,3832-3849.
31. X. Han, B. M. Stoltz, E. J. Corey, J. Am. Chem. Soc. 1999,121, 7600-7605.
32. a) H. E. Simmons, R. D. Smith, J. Am. Chem. Soc. 1958,80, 5323-5324;
33. b) H. E. Simmons, R. D. Smith, J. Am. Chem. Soc. 1959,81, 4256-4264.
34. The structures of diastereomers 16 and 17 were inferred onthe basis of the corresponding cycloheptadienes (i.e. 7a and 8a)that were obtained after the divinylcyclopropane rearrangement.
35. The structure of the tricycle was confirmed by X-ray crystallography of aderivative (ii; TBHP = tert-butyl hydroperoxide). CCDC 719055 contains thesupplementary crystallographic data for this paper. These data can be obtainedfree of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk/data request/cif.
36. For a discussion, see: a) M. P. Schneider, A. Rau, J. Am. Chem.Soc. 1979, 101, 4426-4427;
37. b) Ref. [15].
38. H. M. L. Davies, D. G. Stafford, B. D. Doan, J. H. Houser, J. Am.Chem. Soc. 1998, 120, 3326-3331.
39. For earlier examples of parallel kinetic resolution using diazosubstrates and rhodium-catalysis, see: a) M. P. Doyle, A. B. Dyatkin, A. V.Kalinin, D. A. Ruppar, S. F. Martin, M. R. Spaller, S. Liras, J. Am. Chem.Soc. 1995, 117, 11021-11022;
40. b) H. M. L. Davies, A. M. Walji, Angew. Chem. 2005,117, 1761-1763;
41. Angew. Chem. Int. Ed. 2005, 44, 1733-1735.
42. H. M. L. Davies, P. W. Hougland, W. R. Cantrell, Jr., Synth.Commun. 1992, 22, 971-978.
43. See the Supporting Information for details.
44. Davies has shown convincingly that the initial cyclopropanation usingvinyldiazoacetates proceeds with excellent levels of diastereoseletivity toyield vinyl cylcopropane intermediates possessing the vinyl group on the endoface, see: H. M. L. Davies, T. J. Clark, L. Church, Tetrahedron Lett.1989, 30, 5057-5060.
45. Diene 9 b was determined to be a single diastereomer by HPLCanalysis.
46. 4] as catalyst, were inferred by comparison to analogous studies withenantioen-riched diene substrates (i.e. (+)-9b and (-)-9b; Scheme7). For details, see the Supporting Information.
47. The formation of 7b and 8b in 1:1 d.r. points to comparablereaction rates for the enantiomers of 9 b