Direct, chemoselective N-teri-prenylation of indoles by C-H functionalization

Angewandte Chemie - International Edition

Volumn 48, Issue 38, 2009, Pages 7025-7029

  Luzung, Michael R ^a,b   Lewis, Chad A ^a,b   Baran, Phil S ^a,b  

^a Department of Chemistry ^*  (United States)

^b SCRIPPS RESEARCH INSTITUTE   (United States)

Author keywords

C H functionalization; Indoles; Prenylation; Synthetic methods

Indexed keywords

ANTI-FUNGAL; C-H FUNCTIONALIZATION; CHEMOSELECTIVE; FORMAL SYNTHESIS; GRAM SCALE; INDOLES; NATURAL PRODUCTS; PRENYLATION; SYNTHETIC METHODS;

AMINES; FUNCTIONAL GROUPS; OLEFINS; PALLADIUM;

SYNTHESIS (CHEMICAL);

INDOLE ALKALOID;

ARTICLE; CHEMISTRY; HYDROGEN BOND; PRENYLATION; SYNTHESIS;

HYDROGEN BONDING; INDOLE ALKALOIDS; PRENYLATION;

EID: 70349925244     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200902761     Document Type: Article

References (70)

1. For prenylated indole alkaloid reviews, see a) R. M. Williams, E. M. Stocking, J. F. Sanz-Cervera, Top. Curr. Chem. 2000, 209, 97-173;
2. b) U Scholz, E. Winterfeldt, Nat. Prod. Rep. 2000, 17, 349-366.
3. a) P. S. Baran, C. A. Guerrero, N. B. Ambhaikar, B. D. Hafensteiner, Angew. Chem. 2005, 117, 612-615;
4. Angew. Chem. Int. Ed. 2005, 44, 606-609;
5. P.S. Baran, C.A. Guerrero, N.B. Ambhaikar, B. D. Hafensteiner, Angew. Chem. 2005, 117, 612615;
6. b)P. S. Baran, C. A. Guerrero, B. D. Hafensteiner, N.B. Ambhaikar, Angew. Chem. 2005, 117, 3960-3963;
7. Angew. Chem. Int. Ed. 2005, 44, 3892-3895;
8. c) P. S. Baran, B. D. Hafensteiner, N B. Ambhaikar, C. A. Guerrero, J. D. Gallagher, J.Am. Chem. Soc. 2006, 128, 8678-8693.
9. P. S. Baran, E. J. Corey, J. Am. Chem. Soc. 2002, 124, 7904-7905.
10. a) S. Takase, Y Kawai, I. Uchida, H. Tanaka, H. Aoki, Tetrahedron 1985, 41, 3037-3048;
11. b) G. H. Tan, X. Zhu, A. Ganesan, Org. Lett. 2003, 5, 1801-1803;
12. c) P. López-Alvarado, E. Caballero, C. Avendaño, J.C.Menéndez, Org. Lett. 2006, 5, 4303-4306.
13. a) S. P. Marsden, K. M. Depew, S. J. Danishefsky, J. Am. Chem. Soc. 1994, 116, 11143-11144;
14. b) M. Kimura, M. Futamata, R. Mukai, Y. Tamaru, J. Am. Chem. Soc. 2005, 127, 4592-4593.
15. a) K. M. Depew, S. J. Danishefsky, N. Rosen, L. Sepp-Lorenzino, J. Am. Chem. Soc. 1996, 118, 12463-12464;
16. b) S. Zhao, T Gan, P. Yu, J.M. Cook, Tetrahedron Lett. 1998, 39, 7009-7012.
17. J. M. Schkeryantz, J. C. Woo, S. J. Danishefsky, J. Am. Chem. Soc. 1995, 117, 7025-7026.
18. For a direct enzymatic prenylation at N-1 using prenyltransferases, see H. Zou, X. Zheng, S.-M. Li, J. Nat. Prod. 2009, 72, AA52.
19. For a creative route to .N-tert-prenylindoles by tandem amination of a doubly halogenated styrene, see: A. J. Fletcher, M. N Bax, M. C. Willis, Chem. Commun. 2007, 4764-4766. For insight into the installation of the prenyl unit in indole alkaloid biosynthesis,
20. see C. J. Balibar, A. R. Howard-Jones, C. T. Walsh, Nat. Chem. Biol. 2007, 3, 584-592.
21. a) H. Sugiyama, F. Yokokawa, T. Aoyama, T. Shioiri, Tetrahedron Lett. 2001, 42, 7277-7280;
22. b) F. Yokokawa, H. Sugiyama, T. Aoyama, T. Shioiri, Synthesis 2004, 9, 1476-1480;
23. c) P. S. Baran, C. A. Guerrero, E. J. Corey, J. Am. Chem. Soc. 2003, 125, 5628-5629;
24. d) H. Sugiyama, T Shioiri, F. Yokokawa, Tetrahedron Lett. 2002, 43, 3489-3492;
25. e) G Delia Sala, D. Capozzo, I. Izzo, A. Giordano, A. Iommazzo, A. Spinella, Tetrahedron Lett. 2002, 43, 8839-8841.
26. For reviews on palladium-catalyzed C-H activations,
27. see a) J. Tsuji, Palladium Reagents and Catalysts, Wiley, New York, 1995;
28. b) V. Ritleng, C. Sirlin, M. Pfeffer, Chem. Rev. 2002, 102, 1731-1770;
29. c) S. S. Stahl, Angew. Chem. 2004, 116, 3480-3501;
30. Angew. Chem. Int. Ed. 2004, 43, 3400-3420;
31. d) H. Grennberg, J.-E. Bäckvall, in Transition Metals for Organic Synthesis, Vol.2 (Eds. : M. Beller, C. Bolm), Wiley-VCH, Weinheim, 2004, pp. 243 - 255 ;
32. e) J.-Q. Yu, R. Giri. X. Chen, Org. Biomol. Chem. 2006, 4, 4041 4047.
33. For examples of nucleophilic prenylation processes,
34. see: a) H.M. Chang, C.-H. Cheng, Org. Lett. 2000, 2, 3439-3442;
35. b) T.-P. Loh, J.-R. Zhou, Z. Yin, Org. Lett. 1999, 1, 1855-1857;
36. c) H.-S. Cheng, T.-P. Loh, Z Am. Chem. Soc. 2003, 125, 4990-4991;
37. d) S. E. Denmark, J.Fu, M. J. Lawler, J. Org. Chem. 2006, 71, 1523 -1536;
38. e) S. B. Han, I. S. Kim, H. Han, M. J. Krische, Z Am. Chem. Soc. 2009, 131, 6916-6917.
39. a)T. Itahara, Z Chem. Soc. Chem. Commun. 1981, 254-255;
40. b)D. R. Stuart, K. Fagnou, Science 2007, 316, 1172-1175;
41. c) D. R. Stuart, E. Villemure, K. Fagnou, Z. Am. Chem. Soc. 2007, 129, 12072-12073 ;
42. d) for indole coupling with aryl iodides,
43. see B. S. Lane, M. A. Brown, D. Sames, Z Am. Chem. Soc. 2005, 127, 8050-8057;
44. e) for indole couping with aryl iodonium salts,
45. see N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 4972-4973.
46. N.P. Grimster, C. Gauntlett, C. R. A. Godfrey, M. J. Gaunt, Angew. Chem. 2005, 117, 3185-3189;
47. Angew. Chem. Int. Ed. 2005, 44, 3125-3129.
48. a) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578-9579;
49. b) E. M. Ferreira, H. Zhang, B. M. Stoltz, Tetrahedron 2008, 64, 5987-6001.
50. For direct cross-coupling C-N arylations,
51. see a) G. Mann, J.F. Hartwig, M. S. Driver, C. Fernández-Rivas, J. Am. Chem. Soc. 1998, 120, 827-828;
52. b) J. F. Hartwig, M. Kawatsura, S. I. Hauck, K. H. Shaughnessy, L. M. Alcazar-Roman, Z Org. Chem. 1999, 64, 5575-5580.
53. a) For the first Pd-catalyzed allylic C-H amination, an insightful discussion of its mechanism, and its use in total synthesis,
54. see C. H. Heathcock, J. A. Stafford, D. L. Clark, J. Org. Chem. 1992, 57, 2575-2585;
55. b) for a review of Aza-Wacker oxidative aminations,
56. see: V. Kotov, C. C. Scarborough, S. S. Stahl, Inorg. Chem. 2007, 46, 1910-1923;
57. c) K. J. Fraunhoffer, M. C. White, Z Am. Chem. Soc. 2007, 129, 7274-7276.
58. a) For allylic amination of cyclic olefins,
59. see J. L. Brice, J. E. Harang, V. I. Timokhin, N R. Anastasi, S. S. Stahl, J. Am. Chem. Soc. 2005, 127, 2868-2869;
60. b) for allylic amination of terminal olefins, see S. A. Reed, M. C. White, Z. Am. Chem. Soc. 2008, 130, 3316-3318.
61. C. C. Scarborough, S. S. Stahl, Org. Lett. 2006, 5, 3251-3254.
62. M. Wasa, J.-Q. Yu, J. Am. Chem. Soc. 2008, 130, 14058-14059.
63. L. M. Levy, G. M. Cabrera, J. E. Wright, A. M. Seldes, Phytochemistry 2000, 54, 941-943.
64. B.-L. Lin, J.A. Labinger, J.E. Bercaw, Can. J.Chem. 2009, 57, 264-271.
65. We are grateful to a referee for pointing out that the formation of a C-3-bound silver intermediate followed by transmetalation and 3, 3-rearrangement may also account for the observed product.
66. 3CN (1000 mol %, a toxic expensive reagent that releases HCN), CuCl (10mol%), 2-acetoxy-2methyl-3-butyne (110mol%), DDQ (105mol%), and Pd (10mol%). It also requires four separate purifications (silica gel) and the associated cost of time, labor, and solvent.
67. For examples, see a) I. D. G. Watson, A. K. Yudin, J. Am. Chem. Soc. 2005, 127, 17516-17529;
68. b) I. Dubovyk, I. D G Watson, A. K. Yudin, Z Am. Chem. Soc. 2007, 129, 14172-14173;
69. c) L. M. Stanley, J.F. Hartwig, J. Am. Chem. Soc. 2009, 131, 8971-8983;
70. d) B. M. Trost, M. L. Crawley, Chem. Rev. 2003, 103, 2921-2943, sand references therein.