Palladium-catalyzed intramolecular hydroalkylation of alkenyl- β-keto esters, α-aryl ketones, and alkyl ketones in the presence of Me 3SiCl or HCI

Chemistry - A European Journal

Volumn 10, Issue 24, 2004, Pages 6333-6342

  Han, Xiaoqing ^a   Wang, Xiang ^a   Pei, Tao ^a   Widenhoefer, Ross A ^a  

^a DUKE UNIVERSITY   (United States)

Author keywords

C C coupling; Cyclization; Enols; Homogeneous catalysis; Palladium

Indexed keywords

ALKYLATION; CATALYSIS; ESTERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLEFINS; PALLADIUM COMPOUNDS; REACTION KINETICS; STOICHIOMETRY; SUBSTITUTION REACTIONS;

DIOXANES; INTRAMOLECULAR HYDROALKYLATION; REGIOSELECTIVITY;

STEREOCHEMISTRY;

ESTER DERIVATIVE; HYDROCHLORIC ACID; KETONE DERIVATIVE; PALLADIUM; POLYCYCLIC AROMATIC HYDROCARBON DERIVATIVE; SILICON DERIVATIVE;

ALKYLATION; ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; CHEMICAL MODIFICATION; CHEMICAL REACTION KINETICS; CIS TRANS ISOMERISM; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OLEFINATION; QUANTUM YIELD; REACTION ANALYSIS; STOICHIOMETRY;

EID: 10944238824     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400459     Document Type: Article

References (59)

1. T. Pei, R. A. Widenhoefer, J. Am. Chem. Soc. 2001, 123, 11290.
2. H. Qian, T. Pei, R. A. Widenhoefer, Organometallics, 2004, 23, in press.
3. T. Pei, X. Wang, R. A. Widenhoefer, J. Am. Chem. Soc. 2003, 125, 648.
4. C. Liu, X. Wang, T. Pei, R. A. Widenhoefer, Chem. Eur. J. 2004, 10, DOI: 10.1002/chem.200400460.
5. H. Qian, R. A. Widenhoefer, J. Am. Chem. Soc. 2003, 125, 2056.
6. F. G. Bordwell, Acc. Chem. Res. 1988, 21, 456.
7. M. Bassetti, B. Cerichelli, B. Floris, Tetrahedron 1988, 44, 2997.
8. J. P. Guthrie, Can. J. Chem. 1979, 57, 1177.
9. J. P. Guthrie, P. A. Cullimore, Can. J. Chem. 1979, 57, 240.
10. Portions of this work have been communicated: a) T. Pei, R. A. Widenhoefer, Chem. Commun. 2002, 650; b) X. Wang, T. Pei, X. Han, R. A. Widenhoefer, Org. Lett. 2003, 5, 2699.
11. Portions of this work have been communicated: a) T. Pei, R. A. Widenhoefer, Chem. Commun. 2002, 650; b) X. Wang, T. Pei, X. Han, R. A. Widenhoefer, Org. Lett. 2003, 5, 2699.
12. a) M. Toyota, T. Wada, K. Fukumoto, M. Ihara, J. Am. Chem. Soc. 1998, 120, 4916;
13. b) M. Toyota, A. Ilangovan, R. Okamoto, T. Masaki, M. Arakawa, M. Ihara, Org. Lett. 2002, 4, 4293.
14. a) A. S. Kende, B. Roth, P. J. Sanfilippo, T. J. Blacklock, J. Am. Chem. Soc. 1982, 104, 5808;
15. b) A. S. Kende, B. Roth, P. J. Sanfilippo, J. Am. Chem. Soc. 1982, 104, 1784;
16. c) A. S. Kende, D. J. Wustrow, Tetrahedron Lett. 1985, 26, 5411;
17. d) Y. Ito, H. Aoyama, T. Hirao, A. Mochizuki, T. Saegusa, J. Am. Chem. Soc. 1979, 101, 494;
18. e) Y. Ito, H. Aoyama, T. Saegusa, J. Am. Chem. Soc. 1980, 102, 4519;
19. f) M. Shibasaki, T. Mase, S. Ikegami, J. Am. Chem. Soc. 1986, 108, 2090;
20. g) M. Toyota, T. Seishi, K. Fukumoto, Tetrahedron Lett. 1993, 34, 5947;
21. h) M. Toyota, Y. Nishikawa, K. Motoki, N. Yoshida, K. Fukumoto, Tetrahedron Lett. 1993, 34, 6099;
22. i) K. Irie, T. Isaka, Y. Iwata, Y. Yanai, Y. Nakamura, F. Koizumi, H. Ohigashi, P. A. Wender, Y. Satomi, H. Nishino, J. Am. Chem. Soc. 1996, 118, 10733;
23. j) A. S. Kende, P. J. Sanfilippo, Synth. Commun. 1983, 13, 715;
24. k) L. E. Torres, G. L. Larson, Tetrahedron Lett. 1986, 27, 2223;
25. l) A. S. Kende, B. Roth, P. J. Sanfilippo, J. Am. Chem. Soc. 1982, 104, 1784.
26. a) K. Maeyama, N. Iwasawa, J. Am. Chem. Soc. 1998, 120, 1928;
27. b) N. Iwasawa, K. Maeyama, H. Kusama, Org. Lett. 2001, 3, 3871.
28. M. Yamaguchi, A. Hayashi, M. Hirama, J. Am. Chem. Soc. 1993, 115, 3362.
29. K.-I. Imamura, E. Yoshikawa, V. Gevorgyan, Y. Yamamoto, Tetrahedron Lett. 1999, 40, 4081.
30. In accord with this hypothesis, methyl 3-(triethylsilyloxy)-2,6- heptadienoate underwent rapid desilylation in the presence of 2 without formation of detectable amounts of cyclized product.
31. 2 at 55°C in the absence of 2 led to no detectable cyclization after 12 h.
32. a) F. R. Hartley, Chem. Rev. 1973, 73, 163;
33. b) H. Kurosawa, T. Majima, N. Asada, J. Am. Chem. Soc. 1980, 102, 6996.
34. 1H NMR spectrum; b) Sadtler Standard Carbon-13 NMR Spectra 1986, 17926c; c) K. W. Baldry, M. J. T. Robinson, Tetrahedron 1977, 33, 1663; d) L. Bassi, B. Joos, P. Gassmann, H.-P. Kaiser, H. Leuenberger, W. Keller-Schierlein, Helv. Chim. Acta 1983, 66, 92.
35. 1H NMR spectrum; b) Sadtler Standard Carbon-13 NMR Spectra 1986, 17926c; c) K. W. Baldry, M. J. T. Robinson, Tetrahedron 1977, 33, 1663; d) L. Bassi, B. Joos, P. Gassmann, H.-P. Kaiser, H. Leuenberger, W. Keller-Schierlein, Helv. Chim. Acta 1983, 66, 92.
36. 1H NMR spectrum; b) Sadtler Standard Carbon-13 NMR Spectra 1986, 17926c; c) K. W. Baldry, M. J. T. Robinson, Tetrahedron 1977, 33, 1663; d) L. Bassi, B. Joos, P. Gassmann, H.-P. Kaiser, H. Leuenberger, W. Keller-Schierlein, Helv. Chim. Acta 1983, 66, 92.
37. 2.
38. a) C. P. Casey, CR. Cyr, J. A. Grant, Inorg. Chem. 1974, 13, 910;
39. b) J. Schwartz, J. A. Labinger, Angew. Chem. Int. Ed. 1976, 88, 402; Angew Chem. Int. Ed. Engl. 1976, 15, 333.
40. b) J. Schwartz, J. A. Labinger, Angew. Chem. Int. Ed. 1976, 88, 402; Angew Chem. Int. Ed. Engl. 1976, 15, 333.
41. These arguments are based on those initially forwarded by Reetz: M. T. Reetz, I. Chatziiosifidis, K. Schwellnus, Angew. Chem. 1981, 93, 716; Angew. Chem. Int. Ed. Engl. 1981, 20, 687.
42. These arguments are based on those initially forwarded by Reetz: M. T. Reetz, I. Chatziiosifidis, K. Schwellnus, Angew. Chem. 1981, 93, 716; Angew. Chem. Int. Ed. Engl. 1981, 20, 687.
43. A. Tenaglia, F. Kammerer, Synlett 1996, 576.
44. X. Han, R. A. Widenhoefer, J. Org. Chem. 2004, 69, 1738.
45. J. Yu, M. J. Gaunt, J. B. Spencer, J. Org. Chem. 2002, 67, 4627.
46. a) J. F. Harrod, A. J. Chalk, J. Am. Chem. Soc. 1966, 88, 3491;
47. b) R. Cramer, R. V. Lindsey, J. Am. Chem. Soc. 1966, 88, 3534;
48. c) D. Bingham, B. Hudson, D. E. Webster, P. B. Wells, J. Chem. Soc. Dalton Trans. 1974, 1521;
49. d) A. Sen, T.-W. Lai, Inorg. Chem. 1981, 20, 4036.
50. 8]dioxane. Hexamethyldisiloxane and HCl were identified by comparison to authentic samples.
51. a) B. H. Lipshutz, D. Pollart, J. Monforte, H. Kotsuki, Tetrahedron Lett. 1985, 26, 705;
52. b) N. S. Wilson, B. A. Keay, J. Org. Chem. 1996, 61, 2918.
53. 2 at 70°C in a sealed tube in the absence of 2 led to no detectable reaction after 12 h.
54. J. R. Keefe, A. J. Kresge, in The Chemistry of Enols (Ed.: Z. Rappoport), Wiley, New York, 1990, pp. 451-453.
55. [30] For this reason, HCl does not affect the rate of the conversion of 1 to 3 catalyzed by 2. Because HCl does not affect the equilibrium concentration of enol-I relative to keto-I, this mechanism requires that conversion of enol-I to II must be fast relative to the ketonization of enol-I to regenerate keto-I. In other words, this mechanism predicts that enolization of keto-I is the turnover-limiting step in the palladium-catalyzed hydroalkylation of alkenyl-β-keto esters, α-aryl ketones, and alkyl ketones.
56. B. B. Wayland, R. F. Schramm, Inorg. Chem. 1969, 8, 971.
57. F. Johnson, K. G. Paul, D. Favara, J. Org. Chem. 1982, 47, 4254.
58. B. Gabriele, G. Salerno, F. De Pascali, M. Costa, G. P. Chiusoli, J. Organomet. Chem. 2000, 593-594, 409.
59. L. S. Hegedus, R. E. Williams, M. A. Mcguire, T. Hayashi, J. Am. Chem. Soc. 1980, 102, 4973.