Synthesis and insect antifeedant activity of C-2 and C-5 substituted perhydrofurofurans and 3a-hydroxy-perhydrofurofurans (Part I)

Tetrahedron

Volumn 55, Issue 36, 1999, Pages 11051-11076

  Klein Gebbinck, Edwin A ^a   Bouwman, Catharina T ^a   Bourgois, Magalie ^a   Jansen, Ben J M ^a   De Groot, Aede ^a  

^a WAGENINGEN UNIVERSITY   (Netherlands)

Author keywords

Alkylation; Antifeedants; Cyano compounds; Furofuranes

Indexed keywords

AZADIRACHTIN; CLERODANE DERIVATIVE; CLERODIN; FURAN DERIVATIVE; INSECTICIDE; NITRILE; PERHYDROFURAN DERIVATIVE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION; CHEMICAL STRUCTURE; DIASTEREOISOMER; HYPOTHESIS; INSECT CONTROL; PRIORITY JOURNAL; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOISOMERISM; STRUCTURE ACTIVITY RELATION; SYNTHESIS;

INSECTA; PIERIS BRASSICAE; STAPHYLOCOCCUS PHAGE 3A;

EID: 0033520209     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)00613-4     Document Type: Article

References (51)

1. For a comprehensive compilation of antifeeding clerodane diterpenoids and related compounds, see: E.A. klein Gebbinck, Ph.D. thesis, Wageningen Agricultural University, 1999, chapter 2.
2. (a) S.V. Ley, D. Neuhaus, N.S. Simpkins, and A.J. Whittle, J. Chem. Soc. Perkin Trans. I 1982, 2157-2162;
3. (b) R.B.M. Geuskens, J.M. Luteyn, and L.M. Schoonhoven, Experientia 1983, 39, 403-404;
4. (c) W.M. Blaney, M.S.J. Simmonds, S.V. Ley, and P.S. Jones, Entomol. Exp. Appl. 1988, 46, 267-274;
5. (d) W.M. Blaney, A.C. Cuñat, S.V. Ley, F.J. Montgomery, and M.S.J. Simmonds, Tetrahedron Lett. 1994, 35, 4861-4864.
6. Y. Kojima and N. Kato, Tetrahedron 1981, 37, 2527-2538; Y. Kojima and N. Kato, Nippon Kagaku Kaishi 1981, 712-720.
7. Y. Kojima and N. Kato, Tetrahedron 1981, 37, 2527-2538; Y. Kojima and N. Kato, Nippon Kagaku Kaishi 1981, 712-720.
8. For reviews regarding the biological activity of azadirachtin, see: (a) A.J. Mordue (Luntz) and A. Blackwell, J. Insect Physiol. 1993, 39, 903-924;
9. (b) T.A. van Beek and Ae. de Groot, Recl. Trav. Chim. Pays-Bas 1986, 705, 513-527;
10. (c) S.V. Ley, A.A. Denholm, and A. Wood, Nat. Prod. Reports 1993, 109-157.
11. W.M. Blaney, M.S.J. Simmonds, S.V. Ley, J.C. Anderson, S.C. Smith, and A. Wood, Pestic. Sci. 1994, 40, 169- 173.
12. S.V. Ley, D. Santafianos, W.M. Blaney, and M.S.J. Simmonds, Tetrahedron Lett. 1987, 28, 221-224.
13. (a) S.V. Ley, J.C. Anderson, W.M. Blaney, P.S. Jones, Z. Lidert, E.D. Morgan, N.G. Robinson, D. Santafianos, M.S.J. Simmonds, and P.L. Toogood, Tetrahedron 1989, 45, 5175-5192;
14. (b) R.B. Yamasaki and J.A. Klocke, J. Agric. Food Chem. 1987, 35, 467-471;
15. (c) E.D. Morgan, Strategy in the isolation of insect control substances from plants. In: H. Schmutterer, K.R.S. Ascher and H. Rembold (Eds.), Natural pesticides from the Neem tree (Azadirachta Indica A. Juss.), Proc. 1st Int. Neem Conf., Rottach-Egem, June 1980, GTZ, 1981, p. 43-52;
16. (d) M.S.J. Simmonds, W.M. Blaney, S.V. Ley, J.C. Anderson, R. Bäntali, A.A. Denholm, P. Green, R.B. Grossman, C. Gutteridge, L. Jennens, S.C. Smith, P.L. Toogood, and A. Wood, Entomol. Exp. Appl. 1995, 77, 69-80.
17. (a) A similar analog has also been proposed and synthesized by Lallemand and coworkers, ref. 9b. However, see also ref. 10.
18. (b) During the preparation of this manuscript the first examples of clerodanes with a 3a-hydroxy-furo[2,3b]furan substituent appeared in the literature: H. Kizu, N. Sugita, and T. Tomimori, Chem. Pharm. Bull. 1998, 46, 988-1000.
19. Only a few syntheses of 3a-hydroxy-furo[2,3b]furan-based compounds have been reported; (a) M. Jalali-Naini and J.Y. Lallemand, Tetrahedron Lett. 1986, 27, 497-500;
20. (b) A.P. Brunetière, M. Leclaire, S. Bhatnagar, and J.Y. Lallemand, Tetrahedron Lett. 1989, 30, 341-344;
21. (c) E.R. Civitello and H. Rapoport, J. Org. Chem. 1994, 59, 3775-3782.
22. In 1989, Lallemand and coworkers announced that biological tests of such a compound (3a-hydroxy-3a,4,5,6a-tetrahydrofuro[2,3b]furan) were in progress (ref. 9b), but despite an extensive search of the available literature we were not able to find any report of these experiments.
23. J. Vader, H. Sengers, and Ae. de Groot, Tetrahedron 1989, 45, 2131-2142.
24. Prepared via mCPBA oxidation of vinylcyclohexane in 66% yield (bp. 72°C at 15 mmHg).
25. J.C. Anderson, S.V. Ley, D. Santafianos, and R.N. Sheppard, Tetrahedron 1991, 47, 6813-6850, and references cited therein.
26. T. Mandai, K. Hara, T. Nakajima, M. Kawada, and J. Otera, Tetrahedron Lett. 1983, 24, 4993-4996.
27. E. Vedejs and J.E. Telschow, J. Org. Chem. 1976, 41, 740-741.
28. S. Selikson and D.S. Watt, J. Org. Chem. 1975, 40, 267-268.
29. G. Stork and L. Maldonado, J. Am. Chem. Soc. 1971, 93, 5286-5287; Ibid. 1974, 96, 5272-5274.
30. G. Stork and L. Maldonado, J. Am. Chem. Soc. 1971, 93, 5286-5287; Ibid. 1974, 96, 5272-5274.
31. (a) S.D. Rychnovsky, S. Zeller, D.J. Skalitzky, and G. Griesgraber, J. Org. Chem. 1990, 55, 5550-5551;
32. (b) Supplementary material from ref. 18a;
33. (c) S.D. Rychnovsky, G. Griesgraber, S. Zeller, and D.J. Skalitzky, J. Org. Chem. 1991, 56, 5161-5169;
34. (d) S.D. Rychnovsky and G. Griesgraber, J. Org. Chem. 1992, 57, 1559-1563;
35. (e) S.D. Rychnovsky and R.C. Hoye, J. Am. Chem. Soc. 1994, 116, 1753-1765;
36. (f) S.D. Rychnovsky, G. Griesgraber, and J. Kim, J. Am. Chem. Soc. 1994, 116, 2621-2622.
37. M.W. Rathke, J. Am. Chem. Soc. 1970, 92, 3222-3223.
38. B. Cazes and S. Julia, Tetrahedron 1979, 35, 2655-2660.
39. The assignment of the relative stereochemistry of these compounds was based on comparison with spectral data of related cyanohydrin 1,3-acetonides from ref. 18.
40. In test reactions we also used 4-cyano-2,2-dimethyl-6-isopropyl-1,3-dioxane instead of 33, to facilitate comparison with results reported in the literature for this compound (ref. 18a,b).
41. All bases used in the original literature (ref. 18) were tried at least once.
42. Analytical data for this compound are presented in the experimental section.
43. (a) S.D. Rychnovsky and D.J. Skalitzky, Tetrahedron Lett. 1990, 31, 945-948;
44. (b) S.D. Rychnovsky, B. Rogers, and G.J. Yang, J. Org. Chem. 1993, 58, 3511;
45. (c) L.Y. Brezinski, D.D. Levy, and J.W. Leahy, Tetrahedron Lett. 1994, 35, 7601-7604.
46. 13C chemical shift values (d±s.d. in ppm): (a) syn-1,3-diol acetonides with a chair conformation: 19.62±0.39 and 30.02±0.11 (acetonide methyl shifts) and 98.50±0.56 (acetonide acetal shift); (b) anti-acetonides with a twist conformation: 24.70±0.34 (acetonide methyl shifts) and 100.43±0.11 (acetonide acetal shift). Note that for our cyanohydrin 1,3-acetonides the nomenclature (but not the actual configuration) is opposite to the 1,3-diol acetonides, due to the presence of the cyano group which has a higher priority according to the Cahn-Ingold-Prelog system.
47. For a prior application of such a spontaneous cyclization, see ref. 13 and references cited therein.
48. L. Messchendorp, Terpenoid Antifeedants Against Insects: A Behavioural and Sensory Study, Ph.D. thesis, Wageningen Agricultural University, 1998.
49. Some of the model compounds from Figure 4 were also screened for antifeedant activity against other insect species. (a) Compounds 4, 12, 16-19, 50 and 51 were tested with 4th instar larvae of the Colorado potato beetle (Coleoptera: Leptinotarsa decemlineata) on potato leaf discs, using the no-choice bioassay protocol described before (5 mM concentration). None of the compounds tested showed statistically significant activity, except 51 which displayed weak antifeedant activity in the second test period only (1.5-3 h: AI±sem = 15.9±5.5%; p<0.01, Mann-Whitney U test). (b) Compounds 4, 12, 16-19, 19a, 50-52, 54 and 55 were tested against nymphs of the green peach aphid (Homoptera: Myzus persicae) on an artificial diet in a two-choice bioassay (1000 ppm concentration). None of the compounds displayed statistically significant antifeedant activity.
50. L. Messchendorp, J.J.A. van Loon, and G.J.Z. Gols, Entomol. Exp. Appl. 1996, 79, 195-202.
51. K.F. Raffa and J.L. Frazier, Entomol. Exp. Appl. 1988, 46, 93-100.