Differential reactivities of enyne substrates in ruthenium- and palladium-catalyzed cycloisomerizations

Journal of the American Chemical Society

Volumn 132, Issue 26, 2010, Pages 9206-9218

  Trost, Barry M ^a   Gutierrez, Alicia C ^a   Ferreira, Eric M ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; COORDINATION REACTIONS; OLEFINS; ORGANIC SOLVENTS; PALLADIUM; SUBSTRATES; TRANSITION METALS;

COMPLEMENTARY METHODS; CYCLIC OLEFINS; CYCLOISOMERIZATIONS; DIASTEREO-SELECTIVITY; DIASTEREOMERS; DIFFERENTIAL EFFECT; MECHANISTIC PATHWAYS; METALLACYCLES; N ,N-DIMETHYLACETAMIDE; PALLADIUM CATALYSIS; PALLADIUM CATALYST; RUTHENIUM CATALYSIS; TRICYCLIC PRODUCTS;

RUTHENIUM;

ALKENE; DECALIN; N,N DIMETHYLACETAMIDE; PALLADIUM; RUTHENIUM; ALKYNE;

ARTICLE; CATALYSIS; DIASTEREOISOMER; ENZYME SUBSTRATE; STEREOCHEMISTRY; CHEMISTRY; ENZYME SPECIFICITY; STEREOISOMERISM;

ALKYNES; CATALYSIS; PALLADIUM; RUTHENIUM; STEREOISOMERISM; SUBSTRATE SPECIFICITY;

EID: 77954256286     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja103663h     Document Type: Article

References (57)

1. For a review of atom-economic reactions developed in our laboratory, see: Trost, B. M. Acc. Chem. Res. 2002, 35, 695-705
2. For reviews on non-metathesis, ruthenium-catalyzed carbon-carbon bond-forming reactions, see: Trost, B. M., Frederiksen, M. U., and Rudd, M. T. Angew. Chem., Int. Ed. 2005, 44, 6630-6666
3. Trost, B. M., Toste, F. D., and Pinkerton, A. B. Chem. Rev. 2001, 101, 2067-2096
4. Trost, B. M. Science 1991, 254, 1471-1477
5. For reviews on enyne cycloisomerizations, see: Trost, B. M. and Krische, M. J. Synlett 1998, 1-16
6. Trost, B. M. Acc. Chem. Res. 1990, 23, 34-42
7. Michelet, V., Toullec, P. Y., and Genêt, J.-P. Angew. Chem., Int. Ed 2008, 47, 4268-4315
8. Trost, B. M., Ferreira, E. M., and Gutierrez, A. C. J. Am. Chem. Soc. 2008, 130, 16176-16177
9. Herrmann, J. L., Kieczykowski, G. R., and Schlessinger, R. H. Tetrahedron Lett. 1973, 14, 2433-2436
10. Kuwajima, I. and Urabe, H. Org. Synth. 1988, 66, 87-94
11. The deprotonation was complicated by competitive conjugate addition of diisopropylamide into 8, even when using HMPA
12. See Supporting Information.
13. Gill, G. B., Idris, M. S. H., and Kirollos, K. S. J. Chem. Soc., Perkin Trans. 1 1992, 2355-2365
14. Gill, G. B., Idris, M. S. H., and Kirollos, K. S. J. Chem. Soc., Perkin Trans. 1 1992, 2367-2369
15. For a review on approaches to cis-decalins, see: Singh, V., Iyer, S. R., and Pal, S. Tetrahedron 2005, 61, 9197-9231
16. For a review on routes to trans-decalins, see: Varner, M. A. and Grossman, R. B. Tetrahedron 1999, 55, 13867-13886
17. For an elegant, direct method employing β-silyloxy unsaturated nitriles, see: Fleming, F. F., Shook, B. C., Jiang, T., and Steward, O. W. Org. Lett. 1999, 1, 1547-1550
18. Trost, B. M., Tanoury, G. J., Lautens, M., Chan, C., and MacPherson, D. T. J. Am. Chem. Soc. 1994, 116, 4255-4267
19. Trost, B. M., Romero, D. L., and Rise, F. J. Am. Chem. Soc. 1994, 116, 4268-4278
20. Trost, B. M. and Li, Y. J. Am. Chem. Soc. 1996, 118, 6625-6633
21. Analogous olefin isomerization is often observed in intramolecular palladium-catalyzed Heck reactions of cyclic olefins. Silver or thallium salts, commonly employed as additives to suppress these isomerizations, were ineffective. See: Link, J. T. Org. React. 2002, 60, 157-534
22. Cycloheptene 25 was found to be unreactive to our optimized conditions. While 25% conversion to an unidentified product was observed upon heating to 45 °C, none of the desired 7,5-bicycle was formed
23. Fürstner, A., Schlecker, A., and Lehmann, C. W. Chem. Commun. 2007, 4277-4279
24. Schrauzer, G. N. and Glockner, P. Chem. Ber. 1964, 97, 2451-2462
25. Coulson, D. R. J. Org. Chem. 1972, 37, 1253-1254
26. Trost, B. M. and Trost, M. K. Tetrahedron Lett. 1991, 32, 3647-3550
27. Trost, B. M., Yanai, M., and Hoogsteen, K. J. Am. Chem. Soc. 1993, 115, 5294-5295
28. Bajracharya, G. B., Nakamura, I., and Yamamoto, Y. J. Org. Chem. 2005, 70, 892-897
29. Fürstner, A., Davies, P. W., and Gress, T. J. Am. Chem. Soc. 2005, 127, 8244-8245
30. Matsuda, T., Kadowaki, S., Goya, T., and Murakami, M. Synlett 2006, 575-578
31. Chao, K. C., Rayabarapu, D. K., Wang, C.-C., and Cheng, C.-H. J. Org. Chem. 2001, 66, 8804-8810
32. Treutwein, J. and Hilt, G. Angew. Chem., Int. Ed. 2008, 47, 6811-6813
33. Nieto-Oberhuber, C., Lopez, S., and Echavarren, A. M. J. Am. Chem. Soc. 2005, 127, 6178-6179
34. Odabachian, Y. and Gagosz, F. Adv. Synth. Catal. 2009, 351, 379-386
35. Oh, C. H. and Kim, A. Synlett 2008, 777-781
36. Shibata, T., Takami, K., and Kawachi, A. Org. Lett. 2006, 8, 1343-1345
37. Kuninobu, Y., Yu, P., and Takai, K. Chem. Lett. 2007, 36, 1162-1163
38. Mitsudo, T., Kokuryo, K., and Takegami, Y. J. Chem. Soc., Chem. Commun. 1976, 722-723
39. Mitsudo, T., Kokuryo, K., Shinsugi, T., Nakagawa, Y., Watanabe, Y., and Takegami, Y. J. Org. Chem. 1979, 44, 4492-4496
40. Mitsudo, T., Hori, Y., and Watanabe, Y. J. Organomet. Chem. 1987, 334, 157-167
41. Mitsudo, T., Naruse, H., Kondo, T., Ozaki, Y., and Watanabe, Y. Angew. Chem., Int. Ed. Engl. 1994, 33, 580-581
42. Jordan, R. W. and Tam, W. Org. Lett. 2000, 2, 3031-3034
43. Jordan, R. W. and Tam, W. Org. Lett. 2001, 3, 2367-2370
44. Tenaglia, A. and Giordano, L. Synlett 2003, 2333-2336
45. Villeneuve, K. and Tam, W. Organometallics 2006, 25, 843-848
46. Reference 15.
47. Saito, N., Tanaka, Y., and Sato, Y. Organometallics 2009, 28, 669-671
48. Fan, B.-M., Li, X.-J., Peng, F.-Z., Zhang, H.-B., Chan, A. S. C., and Shao, Z.-H. Org. Lett. 2009, 12, 304-306
49. Shen, Q. and Hammond, G. B. J. Am. Chem. Soc. 2002, 124, 6534-6535
50. See ref 18b.
51. The smallest carbocycle that can contain a trans-olefin has been the subject of continuing interest in organic chemistry. While trans -cyclooctene is fairly stable (strain energy ∼16 kcal/mol), trans -cycloheptene is significantly higher in energy (∼27 kcal/mol) and has only been isolated at low temperatures. For a complete discussion, see: Anslyn, E. V. and Dougherty, D. A. Modern Physical Organic Chemistry; University Science Books: New York, NY, 2006.
52. Trost, B. M. and Toste, F. D. J. Am. Chem. Soc. 1999, 121, 9728-9729
53. Trost, B. M. and Toste, F. D. J. Am. Chem. Soc. 2002, 124, 5025-5036
54. These requirements do not apply to the palladium-catalyzed reaction. For example, under palladium catalysis the cycloisomerization of enyne 14 is a facile process (100% conversion, 64% yield, isolated as an inseparable 8:2 mixture of expected bicycle and olefin-isomerized 1,5-diene, unoptimized). See ref 3b for additional examples
55. Still, W. C. and Galynker, I. Tetrahedron 1981, 37, 3981-3996
56. (trans-2-cis-69) = 8.68 kcal/mol. To validate the accuracy of the 3-21G level, one set of calculations was carried out at the higher 6-31G level; the relative energies differences did not change
57. Calculations of the relative equilibrium geometry energies of the products were carried out using Hartree-Fock basis sets at the 3-21G level. To validate the accuracy of the 3-21G level, one set of calculations was carried out at the higher 6-31G level; the relative energies differences did not change