Concise syntheses of insect pheromones using Z-Selective cross metathesis

Angewandte Chemie - International Edition

Volumn 52, Issue 1, 2013, Pages 310-314

  Herbert, Myles B ^a   Marx, Vanessa M ^a   Pederson, Richard L ^b   Grubbs, Robert H ^a  

^a CALIFORNIA INSTITUTE OF TECHNOLOGY   (United States)

^b Materia Inc   (United States)

Author keywords

Insect pheromones; Metathesis; Ruthenium; Seed oil derivatives; Unconjugated dienes

Indexed keywords

CONCISE SYNTHESIS; CROSS METATHESIS; INSECT PHEROMONE; METATHESIS; SYNTHETIC ROUTES; UNCONJUGATED DIENES;

OLEFINS; PEST CONTROL; RUTHENIUM;

HORMONES;

ORGANOMETALLIC COMPOUND; PHEROMONE; RUTHENIUM;

ANIMAL; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CHEMISTRY; INSECT; SYNTHESIS;

ANIMALS; CATALYSIS; INSECTS; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PHEROMONES; RUTHENIUM;

EID: 84871978691     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201206079     Document Type: Article

References (45)

1. D. Pimintel, Chem. Br. 1991, 27, 646.
2. Lepidopteran pheromones fact sheet: http://www.epa.gov/opp00001/chem- search/reg-actions/registration/fs-G-113-01-Sep-01.pdf (accessed 10/2/2012).
3. S. C.Welter, C. Pickel, J. Millar, F. Cave, R. A. Van Steenwyk, J. Dunley, J. Calif. Agric. 2005, 59, 17
4. P. E. Howse, I. D. R. Stevens, O. T. Jones, Insect Pheromones and their Use in Pest Management, Chapman & Hall, New York, 1998, pp. 314-338.
5. R. L. Pederson, I. M. Fellows, T. A. Ung, H. Ishihara, S. P. Hajela, Adv. Synth. Catal. 2002, 344, 728.
6. The syntheses of alkenyl alcohols, acetates, and aldehydes containing a Z olefin using classical approaches have been widely reported, E. A. Petrushkina, V. N. Kalinin, Russ. J. Gen. Chem. 2008, 78, 1897
7. J.-M. Li, J.-P. Yong, H. A. Aisa, Chem. Nat. Compd. 2008, 44, 224
8. Z. A. Chobanyan, Russ. J. Appl. Chem. 2004, 77, 2036
9. A. S. Subbaraman, S. Mithran, V. R. Mamdapur, Molecules 1998, 3, 35
10. K. Maruoka, M. Oishi, H. Yamamoto, J. Am. Chem. Soc. 1996, 118, 2289
11. B. Schaub, G. Blasér, M. Schlosser, Tetrahedron Lett. 1985, 26, 307
12. M. Horiike, M. Tanouchi, C. Hirano, Agric. Biol. Chem. 1978, 42, 1963
13. C. A. Henrick, Tetrahedron 1977, 33, 1845.
14. K. Endo, R. H. Grubbs, J. Am. Chem. Soc. 2011, 133, 8525
15. B. K. Keitz, K. Endo, M. B. Herbert, R. H. Grubbs, J. Am. Chem. Soc. 2011, 133, 9686
16. B. K. Keitz, K. Endo, P. R. Patel, M. B. Herbert, R. H. Grubbs, J. Am. Chem. Soc. 2012, 134, 693
17. B. K. Keitz, A. Fedorov, R. H. Grubbs, J. Am. Chem. Soc. 2012, 134, 2040.
18. Separation of E isomers from the desired Z isomers was beyond the scope of this paper, however, the undesired E pheromone is generally inert for pest control applications. If isolation of the pure Z isomer is necessary, chromatography with silver nitrate has been shown to be effective at this type of separation: C. M. Williams, L. N. Mander, Tetrahedron 2001, 57, 425.
19. U. Biermann, E. Bornscheuer, M. A. R. Meier, J. O. Metzger, H. J. Schäfer, Angew. Chem. 2011, 123, 3938
20. Angew. Chem. Int. Ed. 2011, 50, 3854
21. B. B. Marvey, Int. J. Mol. Sci. 2008, 9, 1393.
22. M. A. R. Meier, J. O. Metzger, U. S. Schubert, Chem. Soc. Rev. 2007, 36, 1788.
23. Alternative methods, including pressurization of the reaction vessel with 1-butene, and a slow stream of 1-butene into the headspace of the reaction vessel, resulted in highly reduced yields and Z selectivity. The cause of this reduced Z selectivity is not known, but will be investigated in due course.
24. A small amount of terminal olefin products derived from ethenolysis of the seed-oil derivatives was generated during the corresponding reaction with 1-hexene as well. The reaction of 9-decenol with 1-butene to produce 7 produced analogous yields and Z selectivities when compared to the reaction of oleyl alcohol and 1-butene.
25. A much larger amount of the undesired homodimer was detected for reaction of 8-nonenyl acetate compared to 8-nonenol.
26. G. Hornyánszky, J. Rohály, L. Novák, Synth. Commun. 2008, 38, 1533
27. A. Ortiz, A. Quesada, A. Sanchez, J. Chem. Ecol. 2004, 30, 991
28. E. D. Matveeva, A. S. Erin, I. F. Leshcheva, A. L. Kurts, Russ. J. Org. Chem. 2000, 36, 765.
29. T.W. Funk, J. Efskind, R. H. Grubbs, Org. Lett. 2005, 7, 187.
30. The Z-selective homodimerization of conjugated 1,3-dienes was recently reported for molybdenum and tungsten olefin metathesis catalysts: E. M. Townsend, R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc. 2012, 134, 11334.
31. This phenomenon was first reported for a Z-selective molybdenum metathesis catalyst: S. C. Marinescu, D. S. Levine, Y. Zhao, R. R. Schrock, A. H. Hoveyda, J. Am. Chem. Soc. 2011, 133, 11512.
32. There are many reported syntheses of compound 20. Selected examples: a) R. Jindal, A. Devi, G. L. Kad, J. Singh, Indian J. Chem. Sect. B 2010, 49, 495
33. D. M. Jones, S. Kamijo, G. B. Dudley, Synlett 2006, 936
34. J. F. Hayes,M. Shipman, H. Twin, J. Org. Chem. 2002, 67, 935.
35. W. Zhigang, Z. Jianfeng, H. Peiqiang, Chin. J. Chem. 2012, 30, 23
36. S.-G. Kim, Synthesis 2009, 2418
37. K. R. Prasad, P. Anbarasan, J. Org. Chem. 2007, 72, 3155
38. A. E. Kounmbis, D. D. Chronopoulos, Tetrahedron Lett. 2005, 46, 4353
39. S. Iwaki, S. Marumo, T. Saito, M. Yamada, K. Katagiri, J. Am. Chem. Soc. 1974, 96, 7842.
40. V. I. Bykov, A. R. Goletiani, T. A. Butenko, E. Sh. Finkelshtein, Dokl. Akad. Nauk 2002, 384, 496
41. V. I. Bykov, T. A. Butenko, E. B. Petrova, E. Sh. Finkelshtein, Tetrahedron 1999, 55, 8249
42. G. A. Tolstikov, V. N. Odinokov, R. I. Galeeva, R. S. Bakeeva, Tetrahedron Lett. 1978, 21, 1857.
43. The moderate yield is not surprising, given that the homodimerization of 4-pentenol has proven to be a difficult reaction. See Ref. [6c].
44. It should be noted that species 23 resembles a number of monounsaturated, unfunctionalized hydrocarbon pheromones, and this synthetic route should enable facile access to such species.
45. D. A. Carlson, M. S. Mayer, D. Z. Sihacek, Science 1971, 176, 174.