Scope and mechanism of the PdII-catalyzed arylation/carboalkoxylation of unactivated olefins with indoles

Chemistry - A European Journal

Volumn 12, Issue 8, 2006, Pages 2371-2382

  Liu, Cong ^a   Widenhoefer, Ross A ^a  

^a DUKE UNIVERSITY   (United States)

Author keywords

C C coupling; Cyclization; Homogeneous catalysis; Indoles; Palladium

Indexed keywords

CATALYST ACTIVITY; COPPER; METHANOL;

C-C COUPLING; HOMOGENEOUS CATALYSTS; INDOLES;

PALLADIUM;

EID: 33644760299     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200500787     Document Type: Article

References (45)

1. L. S. Hegedus, Transition Melais in the Synthesis of Complex Organic Molecules, University Science Books, Sausalito, CA, 1999.
2. a) M. F. Semmelhack, C. Bodurow, J. Am. Chem. Soc. 1984, 106, 1496;
3. b) M. F. Semmelhack, J. J. Bozell, T. Sato, W. Wulff, E. Spiess, A. Zask, J. Am. Chem. Soc. 1982, 104, 5850;
4. c) J. Boukouvalas, G. Fortier, I.-I. Radu, J. Org. Chem. 1998, 63, 916.
5. a) H. Harayama, A. Abe, T. Sakado, M. Kimura, K. Fugami, S. Tanaka, Y. Tamaru, J. Org. Chem. 1997, 62, 2113;
6. b) Y. Tamaru, M. Hojo, Z. Yoshida, J. Org. Chem. 1988, 53, 5731.
7. a) L. S. Hegedus, W. H. Darlington, J. Am. Chem. Soc. 1980, 102, 4980-4983;
8. b) G. M. Wieber, L. S. Hegedus, B. Åkermark, E. T. Michalson, J. Org. Chem. 1989, 54, 4649.
9. a) R. A. Widenhoefer, Pure Appl. Chem. 2004, 76, 671, and references therein;
10. b) C. Liu, X. Wang, T. Pei, R. A. Widenhoefer, Chem. Eur. J. 2004, 10, 6343;
11. c) X. Han, X. Wang, T. Pei, R. A. Widenhoefer, Chem. Eur. J. 2004, 10, 6333;
12. d) H. Qian, T. Pei, R. A. Widenhoefer, Organometallics 2005, 24, 287.
13. E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578.
14. G. Abbiati, E. M. Beccalli, G. Broggini, C. Zoni, J. Org. Chem. 2003, 68, 7625.
15. A preliminary account of these results has been published: C. Liu, R. A. Widenhoefer, J. Am. Chem. Soc. 2004, 126, 10250.
16. Compound 15 was characterized on the basis of its molecular weight (m/z 253) as determined by GC/MS analysis of the crude reaction mixture. Efforts to isolate 15 in pure form were unsuccessful.
17. 2 in methanol under CO that also react under these conditions to ultimately form 14.
18. W. A. Remers, R. K. Brown, in Indoles (Ed.: W. J. Houlihan), Wiley-Interscience, New York, NY, 1972, vol. 25, pp. 70-71.
19. Pyrroles (Ed.: A. R. Jones), Wiley, New York, NY, 1990-1992, vol. 48.
20. a) J. R. Katzer, Molecular sieves II: [program papers]/ACS symposium series, 40, American Chemical Society, Washington, 1977, pp. 16-17;
21. b) C. K. Hersh, Molecular Sieves, Reinhold Pub. Corp., New York, 1961, pp. 50-51.
22. T. C. Flood, in Topics in Stereochemistry, vol. 12, (Ed.: G. L. Geoffroy), Wiley, New York, 1981, p. 83.
23. a) I. Dorange, J. Löfstedt, K. Närhi, J. Franzén, J.-E. Bäckvall, Chem. Eur. J. 2003, 9, 3445;
24. b) A. M. Castano, J.-E. Bäckvall, J. Am. Chem. Soc. 1995, 117, 560.
25. We thank a reviewer for suggesting this alternative mechanism.
26. A. H. Jackson, P. P. Lynch, J. Chem. Soc. Perkin Trans. 2 1987, 1215.
27. a) J. R. Williams, L. R. Unger, J. Chem. Soc. D 1970, 1605;
28. b) A. H. Jackson, A. E. Smith, Tetrahedron 1968, 24, 403.
29. a) A. H. Jackson, P. Smith, Chem. Commun. (London) 1967, 260;
30. b) A. H. Jackson, B. Naidoo, P. Smith, Tetrahedron 1968, 24, 6199.
31. E. Balogh-Hergovich, G. Speier, J. Chem. Soc. Perkin Trans. 1 1986, 2305.
32. I. Pri-Bar, J. K. Stille, J. Org. Chem. 1982, 47, 1215.
33. a) F. Calderazzo, D. B. Dell'Amico, Inorg. Chem. 1981, 20, 1310;
34. b) D. B. Dell'Amico, F. Calderazzo, N. Zandona, Inorg. Chem. 1984, 23, 137.
35. 13C NMR spectrum.
36. [17] Given the mechanism of palladium-catalyzed cyclization/carboalkoxylation, it appears unlikely that an electron-deficient indolyl radical cation would undergo nucleophilic attack on palladium-complexed olefin I faster than a neutral indole would.
37. D. M. Fenton, P. Steinwand, J. Org. Chem. 1974, 39, 701.
38. T. Hosokawa, T. Uno, S. Inui, S.-I. Murahashi, J. Am. Chem. Soc. 1981, 103, 2318.
39. D. Zargarian, H. Alper, Organometallics 1991, 10, 2914.
40. No attempt was made to isolate 24 from this reaction mixture.
41. a) Y.-S. Lin, A. Yamamoto, Organometallics 1998, 17, 3466;
42. b) Y.-S. Lin, A. Yamamoto, Bull. Chem. Soc. Jpn. 1998, 71, 723.
43. Further characterization of IIIb by electrospray mass spectrometry was unsuccessful.
44. 2 at δ = 173.8 ppm.
45. M. G. Banwell, D. A. S. Beck, J. A. Smith, Org. Biomol. Chem. 2004, 2, 157.