Second-generation synthesis of azadirachtin: A concise preparation of the propargylic mesylate fragment

Angewandte Chemie - International Edition

Volumn 48, Issue 7, 2009, Pages 1317-1320

  Boyer, Alistair ^a   Veitch, Gemma E ^a   Beckmann, Edith ^a   Ley, Steven V ^a  

^a UNIVERSITY OF CAMBRIDGE   (United Kingdom)

Author keywords

keto lactones; Asymmetric catalysis; Hetero diels alder reaction; Natural products; Total synthesis

Indexed keywords

CATALYSIS;

ASYMMETRIC CATALYSIS; AZADIRACHTIN; DIELS-ALDER REACTIONS; EFFICIENT SYNTHESIS; ENANTIOSELECTIVE; HETERO DIELS-ALDER REACTION; NATURAL PRODUCTS; SECOND-GENERATION SYNTHESIS; STEREOCENTER; TOTAL SYNTHESIS;

CHEMICAL REACTIONS;

AZADIRACHTIN; LACTONE; LIMONOID; MESYLIC ACID DERIVATIVE;

ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM; SYNTHESIS;

CATALYSIS; LACTONES; LIMONINS; MESYLATES; STEREOISOMERISM;

EID: 60149083232     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200805395     Document Type: Article

References (52)

1. J. H. Butterworth, E. D. Morgan, Chem. Commun. 1968, 23.
2. For reviews, see: a) A. J. Mordue, E. D. Morgan, A. J. Nisbet in Comprehensive Molecular Insect Science: Control, Vol. 6 (Eds.: L.I. Gilbert, K. Iatrou, S. S. Gill), Elsevier, Oxford, 2004;
3. b) A. J. Mordue, M. S. J. Simmonds, S. V. Ley, W. M. Blaney, W. Mordue, M. Nasiruddin, A. J. Nisbet, Pestic. Sci. 1998, 54, 277;
4. c) A. J. Mordue, A. Blackwell, J. Insect Physiol. 1993, 39, 903;
5. d) H. Schmutterer, The Neem Tree, Wiley-VCH, Weinheim, 1995.
6. For a review, see: G. E. Veitch, A. Boyer, S. V. Ley, Angew. Chem. 2008, 120, 9542;
7. Angew. Chem. Int. Ed. 2008, 47, 9402.
8. a) G. E. Veitch, E. Beckmann, B. J. Burke, A. Boyer, S. L. Maslen, S. V. Ley, Angew. Chem. 2007, 119, 7773;
9. Angew. Chem. Int. Ed. 2007, 46, 7629;
10. b) G. E. Veitch, E. Beckmann, B.J. Burke, A. Boyer, C. Ayats, S. V. Ley, Angew. Chem. 2007, 119, 7777;
11. Angew. Chem. Int. Ed. 2007, 46, 7633;
12. c) G. E. Veitch, A. Pinto, A. Boyer, E. Beckmann, J. C. Anderson, S. V. Ley, Org. Lett. 2008, 10, 569.
13. For advanced synthesis studies, see: a) H. Watanabe, T. Wata-nabe, K. Mori, T. Kitahara, Tetrahedron Lett. 1997, 38, 4429;
14. b) T. Fukuzaki, S. Kobayashi, T. Hibi, Y. Ikuma, J. Ishihara, N. Kanoh, A. Murai, Org. Lett. 2002, 4, 2877;
15. c) J. Ishihara, Y. Ikuma, S. Hatakeyama, T. Suzuki, A. Murai, Tetrahedron 2003, 59, 10287;
16. d) K. C. Nicolaou, A. J. Roecker, H. Monenschein, P. Guntupalli, M. Follmann, Angew. Chem. 2003, 115, 3765;
17. Angew. Chem. Int. Ed. 2003, 42, 3637;
18. e) K. C. Nicolaou, P. K. Sasmal, A. J. Roecker, X. W. Sun, S. Mandal, A. Converso, Angew. Chem. 2005, 117, 3509;
19. Angew. Chem. Int. Ed. 2005, 44, 3443;
20. f) K. C. Nicolaou, P. K. Sasmal, T. V. Koftis, A. Converso, E. Loizidou, F. Kaiser, A. J. Roecker, C. C. Dellios, X. W. Sun, G. Petrovic, Angew. Chem. 2005, 117, 3513;
21. Angew. Chem. Int. Ed. 2005, 44, 3447;
22. g) H. Watanabe, N. Mori, D. Itoh, T. Kitahara, K. Mori, Angew. Chem. 2007, 119, 1534;
23. Angew. Chem. Int. Ed. 2007, 46, 1512.
24. a) C. J. Turner, M. S. Tempesta, R. B. Taylor, M. G. Zagorski, J. S. Termini, D. R. Schroeder, K. Nakanishi, Tetrahedron 1987, 43, 2789;
25. b) J. N. Bilton, H. B. Broughton, P. S. Jones, S. V. Ley, Z. Lidert, E. D. Morgan, H. S. Rzepa, R. N. Sheppard, A. M. Z. Slawin, D. J. Williams, Tetrahedron 1987, 43, 2805;
26. c) W. Kraus, M. Bokel, A. Bruhn, R. Cramer, I. Klaiber, A. Klenk, G. Nagl, H. Pöhnl, H. Sadlo, B. Vogler, Tetrahedron 1987, 43, 2817.
27. For full details of the synthesis of azadirachtin, see: S. V. Ley, et al., Chem. Eur. Jr. 2008, 14, 10683.
28. For strategies used to construct the furanacetal portion of azadirachtin, see: a) S. V. Ley, D. Santafianos, W. M. Blaney, M. S. J. Simmonds, Tetrahedron Lett. 1987, 28, 221;
29. b) D. Pflieger, B. Muckensturm, P. C. Robert, M. T. Simonis, J. C. Kienlen, Tetrahedron Lett. 1987, 28, 1519;
30. c) Y. Nishikimi, T. Iimori, M. Sodeoka, M. Shibasaki, J. Org. Chem. 1989, 54, 3354;
31. d) J. C. Anderson, S. V. Ley, Tetrahedron Lett. 1990, 31, 431;
32. e) K. J. Henry, B. Fraser-Reid, J. Org. Chem. 1994, 59, 5128;
33. f) H. Watanabe, T. Watanabe, K. Mori, Tetrahedron 1996, 52, 13939;
34. g) J. Ishihara, T. Fukuzaki, A. Murai, Tetrahedron Lett. 1999, 40, 1907;
35. h) S. V. Ley, Pure Appl. Chem. 2005, 77, 1115.
36. S. Danishefsky, Acc. Chem. Res. 1981, 14, 400.
37. C. F. Morrison, D. J. Burnell, Tetrahedron Lett. 2001, 42, 7367.
38. We only found five publications describing the hetero Diels-Alder reaction of propargylic aldehydes: a) S. Kii, T. Hashimoto, K. Maruoka, Synlett 2002, 931;
39. b) M. Anada, T. Washio, N. Shimada, S. Kitagaki, M. Nakajima, M. Shiro, S. Hashimoto, Angew. Chem. 2004, 116, 2719;
40. Angew. Chem. Int. Ed. 2004, 43, 2665;
41. c) A. K. Unni, N. Takenaka, H. Yamamoto, V. H. Rawal, J. Am. Chem. Soc. 2005, 127, 1336;
42. d) T. Washio, H. Nambu, M. Anada, S. Hashimoto, Tetrahedron: Asymmetry 2007, 18, 2606;
43. e) T. Washio, R. Yamaguchi, T. Abe, H. Nambu, M. Anada, S. Hashimoto, Tetrahedron 2007, 63, 12037.
44. J. L. Luche, J. Am. Chem. Soc. 1978, 100, 2226.
45. a) W. P. Griffith, S. V. Ley, G. P. Whitcombe, A. D. White, J. Chem. Soc. Chem. Commun. 1987, 1625;
46. b) S. V. Ley, J. Norman, W. P. Griffith, S. P. Marsden, Synthesis 1994, 639.
47. The enzyme was purchased from Amano Enzyme Inc. For a similar application, see: K. Sugawara, Y. Imanishi, T. Hashiyama, Tetrahedron: Asymmetry 2000, 11, 4529.
48. D. B. Dess, J. C. Martin, J. Org. Chem. 1983, 48, 4155.
49. L. H. Horsley, Azeotropic Data III, American Chemical Society, Washington, DC, 1973, p. 112.
50. The allylation reaction tolerated the presence of 17.
51. Under a variety of reaction conditions, the TBS then the benzyl ether groups were cleaved while the methyl acetal unit remained intact.
52. L. Yan, D. Kahne, Synlett 1995, 523.