Chiral N-heterocyclic carbenes in natural product synthesis: Application of Ru-catalyzed asymmetric ring-opening/cross-metathesis and Cu-catalyzed allylic alkylation to total synthesis of baconipyrone C

Angewandte Chemie - International Edition

Volumn 46, Issue 21, 2007, Pages 3860-3864

  Gillingham, Dennis G ^a   Hoveyda, Amir H ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

Allylic alkylation; Asymmetric catalysis; N heterocyclic carbenes; Natural products; Olefin metathesis

Indexed keywords

ALLYLIC ALKYLATION; ASYMMETRIC CATALYSIS; N-HETEROCYCLIC CARBENES; NATURAL PRODUCTS; OLEFIN METATHESIS;

ALKYLATION; CATALYSIS; CHIRALITY; COMPLEXATION; RUTHENIUM; SYNTHESIS (CHEMICAL);

OLEFINS;

BACONIPYRONE C; CARBENE; COPPER; DRUG DERIVATIVE; HETEROCYCLIC COMPOUND; HYDROCARBON; METHANE; PYRONE DERIVATIVE; RUTHENIUM; UNCLASSIFIED DRUG;

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

ALKYLATION; CATALYSIS; COPPER; HETEROCYCLIC COMPOUNDS; HYDROCARBONS; METHANE; MOLECULAR STRUCTURE; PYRONES; RUTHENIUM; STEREOISOMERISM;

EID: 34250705242     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200700501     Document Type: Article

References (55)

1. For a general discussion of natural product synthesis and asymmetric catalysis, see: A. H. Hoveyda, Stimulating Concepts in Chemistry (Eds: F. Vögtle, J. F. Stoddart, M. Shibasaki), Wiley-VCH, Weinheim, 2000, pp. 145-162.
2. D. C. Manker, D. J. Faulkner, T. J. Stout, J. Clardy, J. Org. Chem. 1989, 54, 5371-5374.
3. For a review on asymmetric olefin metathesis, see: a) A. H. Hoveyda, Handbook of Metathesis, Vol. 2 (Ed.: R. H. Grubbs), VCH-Wiley, Weinheim, 2003, pp. 128-150;
4. for previous reports on Ru-catalyzed asymmetric olefin metathesis, see: b) T. J. Seiders, D. W. Ward, R. H. Grubbs, Org. Lett. 2001, 3, 3225-3228;
5. c) J. J. Van Veldhuizen, J. S. Kingsbury, S. B. Garber, A. H. Hoveyda, J. Am. Chem. Soc. 2002, 124, 4954-4955;
6. d) J. J. Van Veldhuizen, D. G. Gillingham, S. B. Garber, O. Kataoka, A. H. Hoveyda, J. Am. Chem. Soc. 2003, 125, 12502-12508;
7. e) D. G. Gillingham, O. Kataoka, S. B. Garber, A. H. Hoveyda, J. Am. Chem. Soc. 2004, 126, 12288-12290;
8. f) J. J. Van Veldhuizen, J. E. Campbell, R. E. Giudici, A. H. Hoveyda, J. Am. Chem. Soc. 2005, 127, 6877-6882;
9. g) T. W. Funk, J. M. Berlin, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 1840-1846;
10. h) J. M. Berlin, S. D. Goldberg, R. H. Grubbs, Angew. Chem. 2006, 118, 7753-7757;
11. Angew. Chem. Int. Ed. 2006, 45, 7591-7595;
12. i) R. E. Giudici, A. H. Hoveyda, J. Am. Chem. Soc. 2007, in press.
13. For applications of Mo-catalyzed asymmetric olefin metathesis in natural product synthesis, see: a) S. D. Burke, N. Muller, C. M. Beudry, Org. Lett. 1999, 1, 9720-9721;
14. b) G. S. Weatherhead, G. A. Cortez, R. R. Schrock, A. H. Hoveyda, Proc. Natl. Acad. Sci. USA 2004, 101, 5805-5809;
15. for a review of applications of catalytic olefin metathesis in natural product synthesis, see: c) K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. 2005, 117, 4564-4601;
16. Angew. Chem. Int. Ed. 2005, 44, 4490-4527.
17. For an overview of recent advances in catalytic asymmetric allylic alkylation reactions, see: H. Yorimitsu, K. Oshima, Angew. Chem. 2005, 117, 4509-4513;
18. Angew. Chem. Int. Ed. 2005, 44, 4435-4439.
19. For catalytic AAA reactions promoted by chiral NHC-based complexes, see: a) A. O. Larsen, W. Leu, C. Nieto-Oberhuber, J. E. Campbell, A. H. Hoveyda, J. Am. Chem. Soc. 2004, 126, 11130-11131;
20. b) S. Tominaga, Y. Oi, T. Kato, D. K. An, S. Okamoto, Tetrahedron Lett. 2004, 45, 5585-5588;
21. c) reference [2f];
22. d) S. Okamoto, S. Tominaga, N. Saino, K. Kase, K. Shimoda, J. Organomet. Chem. 2005, 690, 6001-6007;
23. e) Y. Lee, A. H. Hoveyda, J. Am. Chem. Soc. 2006, 128, 15604-15605.
24. Modern Aldol Reactions (Ed.: R. Mahrwald), Wiley-VCH, Weinheim, 2004.
25. I. Paterson, D. Y. Chen, J. L. Aceña, A. S. Franklin, Org. Lett. 2000, 2, 1513-1516.
26. a) C. A. Falciola, K. Tissot-Croset, A. Alexakis, Angew. Chem. 2006, 118, 6141-6144;
27. Angew. Chem. Int. Ed. 2006, 45, 5995-5998;
28. for reactions of activated substrates, see: b) P. J. Goldsmith, S. J. Teat, S. Woodward, Angew. Chem. 2005, 117, 2275-2277;
29. Angew. Chem. Int. Ed. 2005, 44, 2235-2237.
30. For use of trialkylaluminum reagents in Cu-catalyzed asymmetric conjugate additions, see: M. d'Augustin, L. Palais, A. Alexakis, Angew. Chem. 2005, 117, 1400-1402;
31. Angew. Chem. Int. Ed. 2005, 44, 1376-1378.
32. M. K. Brown, T. L. May, C. A. Baxter, A. H. Hoveyda, Angew. Chem. 2007, 119, 1115-1118;
33. Angew. Chem. Int. Ed. 2007, 46, 1097-1100.
34. E. Vedejs, M. Jure, Angew. Chem. 2005, 117, 4040-4069;
35. Angew. Chem. Int. Ed. 2005, 44, 3974-4001.
36. Preliminary studies indicated that a benzyl ether gives rise to side products during AAA; the alcohol was therefore masked as an allyl ether.
37. See the Supporting Information for full experimental details involving synthesis of 13.
38. H. Ito, T. Taguchi, Y. Hanazawa, J. Org. Chem. 1993, 58, 774-775.
39. Chiral Mo catalysts (R. R. Schrock, A. H. Hoveyda, Angew. Chem. 2003, 115, 4740-4782;
40. Angew. Chem. Int. Ed. 2003, 42, 4592-4633) provide 19 with lower enantiomeric purity (≤67 % ee).
41. Prolonged reaction times led to the formation of the acyclic diol as the exclusive product.
42. a) S. J. Connon, S. Blechert, Angew. Chem. 2003, 115, 1944-1968;
43. Angew. Chem. Int. Ed. 2003, 42, 1900-1923;
44. b) A. K. Chatterjee, T.-L. Choi, D. P. Sanders, R. H. Grubbs, J. Am. Chem. Soc. 2003, 125, 11360-11370.
45. Similar observations were made when pyran 21 was used as the substrate.
46. a) P. A. Evans, J. Cui, S. J. Gharpure, A. Polosukhin, H. Zhang, J. Am. Chem. Soc. 2003, 125, 14702-14703;
47. b) T. R. Hoye, B. M. Elkov, J. Jeon, M. Khoroosi, Org. Lett. 2006, 8, 3383-3386.
48. S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 8168-8179.
49. Lower amounts of CuCN (e.g., 20 mol %) led to the formation of substantial amounts of dihydrofuran by-product derived from phosphate displacement by the secondary allylic alcohol. With 1.5 equiv CuCN, about 10 % of this by-product is generated.
50. Previously reported methods for synthesis of γ-pyrones through triketone cyclizations proved to be inefficient; see: a) H. Arimoto, S. Nishiyama, S. Yamamura, Tetrahedron Lett. 1990, 31, 5619-5620;
51. b) T. Lister, M. V. Perkins, Angew. Chem. 2006, 118, 2622-2626;
52. Angew. Chem. Int. Ed. 2006, 45, 2560-2564.
53. K. A. Scheidt, H. Chen, B. C. Follows, S. R. Chemler, D. Coffey, W. R. Roush, J. Org. Chem. 1998, 63, 6436-6437.
54. 4NF) led to low yields owing to decomposition of starting material and/or product.
55. The full scope of the Cu-catalyzed AAA with alkylaluminum reagents will be reported in a separate account.