Palladium-catalyzed intramolecular oxidative alkylation of 4-pentenyl β-dicarbonyl compounds

Chemistry - A European Journal

Volumn 10, Issue 24, 2004, Pages 6343-6352

  Liu, Cong ^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

CARBON; CATALYSIS; ESTERS; ORGANIC COMPOUNDS; OXIDATION; STOICHIOMETRY; SUBSTITUTION REACTIONS; THERMAL EFFECTS;

CYCLIZED PRODUCTS; DICARBONYL COMPOUNDS; INTRAMOLECULAR OXIDATIVE ALKYLATION; PENTENYL CHAINS;

STEREOCHEMISTRY;

CARBONYL DERIVATIVE; ESTER DERIVATIVE; KETONE DERIVATIVE; PALLADIUM;

ALKYLATION; ARTICLE; CATALYSIS; CATALYST; CHEMICAL MODIFICATION; CYCLIZATION; OXIDATION KINETICS; REACTION ANALYSIS; STOICHIOMETRY; TEMPERATURE DEPENDENCE;

EID: 10944270772     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400460     Document Type: Article

References (63)

1. a) R. F. Heck, J. P. Nolley, J. Org. Chem. 1972, 37, 2320;
2. b) T. Mizoroki, K. Mori, A. Ozaki, Bull. Chem. Soc. Jpn. 1971, 44, 581;
3. c) A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379;
4. c) A. de Meijere, F. E. Meyer, Angew. Chem. 1994, 106, 2473; Angew. Chem. Int. Ed. Engl. 1994, 33, 2379;
5. d) J. T. Link, L. E. Overman, in Metal-catalyzed Cross-coupling Reactions (Eds.: F. Diedrich, P. J. Stang), Wiley-VCH, Weinheim, 1998, Chapter 3.
6. S. A. Lebedev, V. S. Lopatina, E. S. Petrov, I. P. Beletskaya, J. Organomet. Chem. 1988, 344, 253.
7. B. P. Branchaud, W. D. Detlefsen, Tetrahedron Lett. 1991, 32, 6273.
8. Y. Ikeda, T. Nakamura, H. Yorimitsu, K. Oshima, J. Am. Chem. Soc. 2002, 124, 6514.
9. T. Fujioka, T. Nakamura, H. Yorimitsu, K. Oshima, Org. Lett. 2002, 4, 2257.
10. a) L. S. Hegedus, Angew. Chem. 1988, 100, 1147; Angew. Chem. Int. Ed. Engl. 1988, 27, 1113;
11. a) L. S. Hegedus, Angew. Chem. 1988, 100, 1147; Angew. Chem. Int. Ed. Engl. 1988, 27, 1113;
12. b) L. S. Hegedus, J. M. McKearin, J. Am. Chem. Soc. 1982, 104, 2444;
13. c) L. S. Hegedus, G. F. Allen, J. J. Bozell, E. L. Waterman, J. Am. Chem. Soc. 1978, 100, 5800;
14. d) 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;
15. e) Y. Tamaru, M. Hojo, H. Higashimura, Z. Yoshida, J. Am. Chem. Soc. 1988, 110, 3994.
16. a) T. Hosokawa, S.-I. Murahashi, Acc. Chem. Res. 1990, 23, 49;
17. b) R. A. T. M. van Benthem, H. Hiemstra, J. J. Michels, W. N. Speckamp, J. Chem. Soc. Chem. Commun. 1994, 3, 357.
18. a) J. Smidt, W. Hafner, R. Jira, J. Sedlmeier, R. Sieber, R. Rüttinger, H. Kojer, Angew. Chem. 1959, 71, 176;
19. b) J. Smidt, W. Hafner, R. Jira, R. Sieber, J. Sedlmeier, A. Sabel, Angew. Chem. 1962, 74, 93; Angew. Chem. Int. Ed. Engl. 1962, 1, 80;
20. b) J. Smidt, W. Hafner, R. Jira, R. Sieber, J. Sedlmeier, A. Sabel, Angew. Chem. 1962, 74, 93; Angew. Chem. Int. Ed. Engl. 1962, 1, 80;
21. c) J. Tsuji, Synthesis 1984, 5, 369.
22. a) L. S. Hegedus, in Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books, Mill Valley, CA, 1999, Chapter 7.2, pp. 188-204;
23. b) L. S. Hegedus, in Organometallics in Synthesis (Ed.: M. Schlosser), Wiley, Chichester, 1994, Chapter 5.3.1, pp. 388-399.
24. a) M. Toyota, T. Wada, K. Fukumoto, M. Ihara, J. Am. Chem. Soc. 1998, 120, 4916;
25. b) M. Toyota, T. Wada, M. Ihara, J. Org. Chem. 2000, 65, 4565;
26. c) M. Toyota, M. Ihara, Synlett 2002, 1211;
27. d) M. Toyota, A. Ilangovan, R. Okamoto, T. Masaki, M. Arakawa, M. Ihara, Org. Lett. 2002, 4, 4293.
28. See also: a) J. Franzén, J.-E. Bäckvall, J. Am. Chem. Soc. 2003, 125, 6056; b) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578; c)G. Abbiati, E. M. Beccalli, G. Broggini, C. Zoni, J. Org. Chem. 2003, 68, 7625.
29. See also: a) J. Franzén, J.-E. Bäckvall, J. Am. Chem. Soc. 2003, 125, 6056; b) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578; c)G. Abbiati, E. M. Beccalli, G. Broggini, C. Zoni, J. Org. Chem. 2003, 68, 7625.
30. See also: a) J. Franzén, J.-E. Bäckvall, J. Am. Chem. Soc. 2003, 125, 6056; b) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578; c)G. Abbiati, E. M. Beccalli, G. Broggini, C. Zoni, J. Org. Chem. 2003, 68, 7625.
31. T. Pei, R. A. Widenhoefer, J. Am. Chem. Soc. 2001, 123, 11 290.
32. H. Qian, R. A. Widenhoefer, J. Am. Chem. Soc. 2003, 125, 2056.
33. H. Qian, R. A. Widenhoefer, Organometallics, 2004, 23, in press.
34. A portion of these results have been communicated: T. Pei, X. Wang, R. A. Widenhoefer, J. Am. Chem. Soc. 2003, 125, 648.
35. 2 led to the formation of chlorinated byproducts. 1,2-Dichloroethane (DCE) proved superior to dioxane as a solvent for the oxidative alkylation of 4-pentenyl β-dicarbonyl compounds.
36. Similar products are formed in the palladium-mediated cyclization of 2-diazo-3-oxo-6-heptenoates: D. F. Taber, J. C. Amedio, R. G. Sherrill, J. Org. Chem. 1986, 51, 3382.
37. J. Christoffers, J. Org. Chem. 1998, 63, 4539.
38. The selectivities quoted here refer to the ratio of oxidative alkylation:hydroalkylation products and therefore differ from the selectivities quoted in Table 1, which refer to the ratio of the desired oxidative alkylation product to all isomerized starting materials.
39. [13,14]
40. 13C NMR analysis required to establish regiochemistry.
41. [22d] b) T. Pei, R. A. Widenhoefer, Chem. Commun. 2002, 6, 650; c) X. Wang, X. Han, T. Pei, R. A. Widenhoefer, Org. Lett. 2003, 5, 2699; d) X. Han, X. Wang, T. Pei, R. A. Widenhoefer, Chem. Eur. J. 2004, 10, DOI: 10.1002/chem.200400459.
42. [22d] b) T. Pei, R. A. Widenhoefer, Chem. Commun. 2002, 6, 650; c) X. Wang, X. Han, T. Pei, R. A. Widenhoefer, Org. Lett. 2003, 5, 2699; d) X. Han, X. Wang, T. Pei, R. A. Widenhoefer, Chem. Eur. J. 2004, 10, DOI: 10.1002/chem.200400459.
43. [22d] b) T. Pei, R. A. Widenhoefer, Chem. Commun. 2002, 6, 650; c) X. Wang, X. Han, T. Pei, R. A. Widenhoefer, Org. Lett. 2003, 5, 2699; d) X. Han, X. Wang, T. Pei, R. A. Widenhoefer, Chem. Eur. J. 2004, 10, DOI: 10.1002/chem.200400459.
44. 1H NMR spectrum.
45. [13,14]
46. 2].
47. 13C NMR spectrum.
48. As an alternative to the formation of intermediate VII from IV, collapse of the enol of IV could displace an anionic palladium chloride species that could then deprotonate the cationic cyclohexenone intermediate to form a Pd(H)Cl species and free 2-cyclohexenone. We thank a reviewer for suggesting this mechanism.
49. 1] to 5a.
50. Data was collected in this manner to avoid potential complications arising from scrambling of the allylic positions.
51. 2 would form in preference to III-CHD. However, because equilibrium isotope effects are typically not large, detectable amounts of III-CHD and hence 12a-CHD would be formed if conversion of III to IV were reversible under reaction conditions.
52. M. Wolfsberg, Acc. Chem. Res. 1972, 5, 225.
53. H. Kurosawa, T. Majima, N. Asada, J. Am. Chem. Soc. 1980, 102, 6996.
54. a) C. P. Casey, C. R. Cyr, J. Grant, A. Inorg. Chem. 1974, 13, 910;
55. b) J. Schwartz, J. A. Lagbinger, Angew Chem. 1976, 88, 402; Angew Chem. Int. Ed. Engl. 1976, 15, 333.
56. b) J. Schwartz, J. A. Lagbinger, Angew Chem. 1976, 88, 402; Angew Chem. Int. Ed. Engl. 1976, 15, 333.
57. S. Mecking, L, K. Johnson, L. Wang, M. Brookhart, J. Am. Chem. Soc. 1998, 120, 888.
58. a) M. Bassetti, B. Cerichelli, G. Floris, Tetrahedron 1988, 44, 2997;
59. b) J. P. Guthrie, Can. J. Chem. 1979, 57, 1177;
60. c) J. P. Guthrie, P. A. Cullimore, Can. J. Chem. 1979, 57, 240.
61. [22c,d]
62. B. B. Wayland, R. F. Schramm, Inorg. Chem. 1969, 8, 971.
63. S. Bernasconi, P. Gariboldi, G. Jommi, M. Sisti, Tetrahedron Lett. 1980, 21, 2337.