Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction

Journal of the American Chemical Society

Volumn 130, Issue 13, 2008, Pages 4517-4526

  Cheong, Paul Ha Yeon ^a   Morganelli, Philip ^b   Luzung, Michael R ^b   Houk, K N ^b   Toste, F Dean ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CROSS-CONJUGATED TRIENES; CYCLOISOMERIZATION; HYDROGEN SHIFT; NUCLEOPHILIC ADDITION;

CATALYST ACTIVITY; COMPLEXATION; CROSSLINKING; ISOMERIZATION; NUCLEOPHILES; REACTION KINETICS;

ORGANIC COMPOUNDS;

ALLENE DERIVATIVE; BORIC ACID; GOLD; GOLD DERIVATIVE; PHOSPHINEGOLD; TRIS(TRIPHENYLPHOSPHINEGOLD)OXONIUM TETRAFLUOROBORATE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; ISOMERIZATION;

ALKADIENES; ALKYNES; CATALYSIS; CYCLIZATION; MODELS, CHEMICAL; MOLECULAR STRUCTURE; ORGANOGOLD COMPOUNDS; STEREOISOMERISM;

EID: 41549152977     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja711058f     Document Type: Article

References (63)

1. Allenyne cycloisomerizations proceeding through metallacyclopentene intermediates: For Rh, (a) Brummond, K. M.; Chen, H.; Sill, P.; You, L. J. Am. Chem. Soc. 2002, 124, 15186.
2. (b) Shibata, T.; Takesue, Y.; Kadowaki, S.; Takagi, K. Synlett 2003, 268.
3. (c) Mukai, C.; Inagaki, F.; Yoshida, T.; Kitagaki, S. Tetrahedron Lett. 2004, 45, 4117.
4. For Ti, (d) Urabe, H.; Takeda, T.; Hideura, D.; Sato, F. J. Am. Chem. Soc. 1997, 119, 11295.
5. For Pt, (e) Cadran, N.; Cariou, K.; Herve, G.; Aubert, C.; Fensterbank, L.; Malacria, M.; Marco-Contelles, J. J. Am. Chem. Soc. 2004, 126, 3408.
6. (f) Matsuda, T.; Kadowski, S.; Goyam, T.; Murakami, M. Synlett 2006, 575.
7. For Mo, (g) Shen, Q.; Hammond, G. B. J. Am. Chem. Soc. 2002, 124, 6534.
8. Alternative mechanisms for allenyne cycloisomerization: For Co, (a) Lierena, D.; Aubert, C.; Malacria, M. Tetrahedron Lett. 1996, 37, 7027.
9. For Ga, (b) Lee, S. I.; Sim, S. H.; Kim, S. M.; Kim, K.; Chung, Y. K. J. Org. Chem. 2006, 71, 7120.
10. For Mo-catalyzed allenyne metathesis, (c) Murakami, M.; Kadowski, S.; Matsuda, T. Org. Lett. 2005, 7, 3953.
11. Thermal reactions of allenynes: (a) Ohno, H.; Mizutani, T.; Kadoh, Y.; Miyamura, K.; Tanaka, T. Angew. Chem., Int. Ed. 2005, 44, 5113.
12. (b) Oh, C. H.; Gupta, A. K.; Park, D. I.; Kim, N. Chem. Commun. 2005, 5670.
13. DFT-based theoretical study of the Pt(II)-catalyzed cycloisomerization of allenynes: Soriano, E.; Marco-Contelles, J. Chem - Eur. J. 2005, 11, 521.
14. Cycloisomerization of 1,5- and 1,6-enynes involving nucleophilic addition of olefins to gold(I)-acetylene complexes: (a) Nieto-Oberhuber, C.; Muñoz, M. P.; Buñuel, E.; Nevado, C.; Cárdenas, D. J.; Echavarren, A. M. Angew. Chem., Int. Ed. 2004, 43, 2402.
15. (b) Mamane, V.; Gress, T.; Krause, H.; Fürstner, A. J. Am. Chem. Soc. 2004, 126, 8654.
16. (c) Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 10858.
17. (d) Nieto-Oberhuber, C.; López, S.; Echavarren, A. M. J. Am. Chem. Soc. 2005, 127, 6178.
18. (e) Gagosz, F. Org. Lett. 2005, 7, 4129.
19. (e) Sun, J.; Conley, M. P.; Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2006, 128, 9705.
20. (f) Fehr, C.; Galindo, J. Angew. Chem., Int. Ed. 2006, 45, 2901.
21. (g) Park, S.; Lee, D. J. Am. Chem. Soc. 2006, 128, 10664.
22. (h) Horino, Y.; Luzung, M. R.; Toste, F. D. J. Am. Chem. Soc. 2006, 128, 11364.
23. For reviews: (i) Nieto-Oberhuber, C.; López, A.; Jiménez-Núñez, E.; Echavarren, A. M. Chem. Eur. J. 2006, 12, 5916.
24. (j) Ma, S.; Yu, S.; Gu, Z. Angew. Chem., Int. Ed. 2006, 45, 200.
25. (a) Lemière, G.; Gandon, V.; Agenet, N.; Goddard, J.-P.; de Kozak, A.; Aubert, C.; Fensterbank, L.; Malacria, M. Angew. Chem., Int. Ed. 2006, 45, 7596.
26. (b) The allyl cation intermediate was trapped by the use of deuterated methanol.
27. (c) Protodemetallations are known to occur stereoselectively. In the case of 1,6-allenyne rearrangements, the same anti incorporation of deuterium was observed.
28. Recent reviews of gold-catalyzed reactions: (a) Jiménez- Núñez, E.; Echavarren, A. M. Chem. Commun. 2007, 333.
29. (b) Gorin, D. J.; Toste, F. D. Nature 2007, 446, 395.
30. (c) Fürstner, A.; Davies, P. W. Angew. Chem., Int. Ed. 2007, 46, 2.
31. (d) Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180.
32. Gupta, A. K.; Rhim, C. Y.; Oh, C. H.; Mane, R. S.; Han, S.-H. Green Chem. 2006, 8, 25.
33. Dipolar cycloadditions catalyzed by a two copper mechanism have been reported recently: Ahlquist, M.; Fokin, V. V. Organometallics 2007, 26, 4389.
34. A related allenyne rearrangement has been reported: Zriba, R.; Gandon, V.; Aubert, C.; Fensterbank, L.; Malacria, M. Chem. - Eur. J. 2008, 14, 1482.
35. A preference for formation of Z-9a can be rationalized by conformational analysis of the proton transfer step. A conformation leading to an E-olefin, placing ethyl planar with phenyl group, introduces a significant strain. The final product distribution of 7:1, corresponding to an energy difference of 1.2 kcal/mol, is an acceptable value for A(1,2)-strain.
36. Both alkyl- (2e) and aryl- (2f) substituted alkynes failed to react under the reported reactions conditions. See Experimental Section for details. (Chemical Equation Presented)
37. In contrast, triphenylphosphine hexafluoroantimonate catalyzed the cycloisomerization of 1,6-allenynes containing phenyl-substituted alkynes via a tandem 5-endo-dig/Nazarov cyclization mechanism: Lin, G.-Y.; Yang, C.-Y.; Liu, R. S. J. Org. Chem. 2007, 72, 6753.
38. Related 6-endo-dig cyclization of allenynes: Zhao, J.; Hughes, C. O.; Toste, F. D. J. Am. Chem. Soc. 2006, 128, 7436.
39. Houk, K. N.; Li, Y.; Evanseck, J. D. Angew. Chem., Int. Ed. 2003, 31, 682.
40. Examples: Doering, W. von E.; Zhao, X. J. Am. Chem. Soc. 2006, 126, 9080 and references therein.
41. CH3 isotope effect of 1.43 was measured in the related Schmittelene cyclization of enyne-allenes: Bekele, T.; Christian, C. F.; Lipton, M. A.; Singleton, D. A. J. Am. Chem. Soc. 2005, 127, 9216.
42. Coordination of cationic triphenylphosphinegold(I) to the internal olefin of the allene does not lead to viable catalysis and therefore was excluded from analyses.
43. 5 proton of the acetylide spectrum at 5.07 ppm.
44. A related dual-activation mechanism has recently been proposed for the copper-catalyzed azide-alkyne cycloaddition: Ahlquist, M.; Fokin, V. V. Organometallics 2007, 26, 4389.
45. Frisch, M. J.; et al. Gaussian 03, Revision C.02; Gaussian, Inc.: Pittsburgh, PA, 2004.
46. Figures prepared with CYLview: Legault, C. Y. CYLview, version 1.0b; UCLA: Los Angeles, CA, 2007.
47. Computational study of copper-catalyzed pericyclic reactions has been reported: Himo, F.; Lovell, T.; Hilgraf, R.; Rostovtsev, V. V.; Noodleman, L.; Sharpless, K. B.; Fokin, V. V. J. Am. Chem. Soc. 2005, 127, 210.
48. Schuster, O.; Liau, R.-Y.; Schier, A.; Schmidbaur, H. Inorg. Chim. Acta 2005, 358, 1429.
49. Oxidative addition of phosphinegold(I)halide complexes to elemental halogens: Schneider, D.; Schier, A.; Schmidbaur, H. Dalton Trans. 2004, 1995 and references therein.
50. CH3 isotope effect (1.19 ± 0.05) is much lower.
51. D isotope effect on β-hydrogen elimination: (a) Ozawa, F.; Ito, T.; Yamamoto, A. J. Am. Chem. Soc. 1980, 120, 6457.
52. (b) Evans, J.; Schwarts, J.; Urquhart, P. W. J. Organomet. Chem. 1974, 81, C37.
53. 5c The analogous intermediate is not accessible in the current reaction as it would require the formation of a strained bicyclo[3.1.0]hex-1-ene species, in violation of Bredt's rule.
54. Reaction of analogous silver acetylides with various Lewis acids yielded no observable triene product.
55. Examples of cycloisomerizations enallenes involving activation of allenes by cationic phosphine gold complexes: (a) Zhang, L. J. Am. Chem. Soc. 2005, 127, 16804.
56. (b) Buzas, A.; Gagosz, F. J. Am. Chem. Soc. 2006, 128, 12614.
57. (c) Lee, J. H.; Toste, F. D. Angew. Chem., Int. Ed. 2007, 46, 912.
58. (d) Huang, X.; Zhang, L. J. Am. Chem. Soc. 2007, 129, 6398.
59. (e) Luzung, M. R.; Mauleón, P.; Toste, F. D. J. Am. Chem. Soc. 2007, 129, 12402.
60. (f) Lemiére, G.; Gandon, V.; Cariou, K.; Fukuyama, T.; Dhimane, A.-L.; Fensterbank, L.; Malacria, M. Org. Lett. 2007, 9, 2207.
61. (g) Tarselli, M. A.; Chianese, A. R.; Lee, S. J.; Gagné, M. R. Angew. Chem., Int. Ed. 2007, 46, 6670.
62. There is a slight preference for the phosphinegold to coordinate to the allene over the alkyne.
63. This was the only case presented in this paper where the KIE was computed by use of a simple phosphine.