Rhodium(III)-catalyzed arene and alkene C-H bond functionalization leading to indoles and pyrroles

Journal of the American Chemical Society

Volumn 132, Issue 51, 2010, Pages 18326-18339

  Stuart, David R ^a,b   Alsabeh, Pamela ^a,c   Kuhn, Michelle ^a   Fagnou, Keith ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

^b HARVARD UNIVERSITY   (United States)

^c DALHOUSIE UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

BIOLOGICAL ACTIVITIES; C-H BOND; DEUTERIUM LABELING; EFFICIENT SYNTHESIS; ENAMIDES; FUNCTIONALIZATIONS; HETEROCYCLES; INDOLE DERIVATIVES; INTERNAL ALKYNES; KINETIC ANALYSIS; MILD TEMPERATURES; OPTIMIZED REACTION CONDITIONS; OXIDATIVE ANNULATION; RHODIUM-CATALYZED; ROOM TEMPERATURE; TERMINAL OXIDANTS;

ACETYLENE; CATALYSIS; DEUTERIUM; FUNCTIONAL GROUPS; MOLECULAR OXYGEN; OLEFINS; POTASSIUM COMPOUNDS; RHODIUM; SYNTHESIS (CHEMICAL);

RHODIUM COMPOUNDS;

ALKENE; INDOLE DERIVATIVE; PAULLONE; POLYCYCLIC AROMATIC HYDROCARBON; PYRROLE DERIVATIVE; RHODIUM COMPLEX;

ANNULATION REACTION; ARTICLE; CATALYSIS; HYDROGEN BOND; OXIDATION; SYNTHESIS;

ALKENES; CATALYSIS; INDOLES; ORGANOMETALLIC COMPOUNDS; PYRROLES; RHODIUM;

EID: 78650613906     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja1082624     Document Type: Article

References (99)

1. A Beilstein search for indoles with biological activity yielded >45 000 results.
2. Richter, J. M., Ishihara, Y., Masuda, T., Whitefield, B. W., Llamas, T., Pohjakallio, A., and Baran, P. S. J. Am. Chem. Soc. 2008, 130, 17938 and references therein
3. Fürstner, A. Angew. Chem., Int. Ed. 2003, 43, 3582
4. Yoon, Z. S., Kwon, J. H., Yoon, M.-C., Koh, M. K., Noh, S. B., Sessler, J. L., Lee, J. T., Seidel, D., Aguilar, A., Shimizu, S., Suzuki, M., Osuka, A., and Kim, D. J. Am. Chem. Soc. 2006, 128, 14128
5. Lee, J.-S., Kang, N.-Y., Kim, Y. K., Samanta, A., Feng, S., Kim, H. K., Vendrell, M., Park, J. H., and Chang, Y.-T. J. Am. Chem. Soc. 2009, 131, 10077
6. Gilchrist, T. L. J. Chem. Soc., Perkin Trans. 1 1999, 2849
7. de Sá Alves, F. R., Barreiro, E. J., and Fraga, C. A. M. Mini-Rev. Med. Chem. 2009, 9, 782
8. For a review on transition metal-catalyzed indole synthesis, see
9. Zeni, G. and Larock, R. C. Chem. Rev. 2006, 106, 4644. For selected individual accounts, see
10. Tida, H., Yuasa, Y., and Kibayashi, C. J. Org. Chem. 1980, 45, 2938
11. Sakamoto, T., Nagano, T., Kondo, Y., and Yamanaka, H. Synthesis 1990, 215
12. Larock, R. C. and Yum, E. K. J. Am. Chem. Soc. 1991, 113, 6689
13. Koerber-Ple, K. and Massiot, G. Synlett 1994, 759
14. Chen, C. Y., Lieberman, D. R., Larsen, R. D., Verhoeven, T. R., and Reider, P. J. J. Org. Chem. 1997, 62, 2676
15. Larock, R. C., Yum, E. K., and Refvik, M. D. J. Org. Chem. 1998, 63, 7652
16. Yamazaki, K., Nakamura, Y., and Kondo, Y. J. Org. Chem. 2003, 68, 6011
17. Watanabe, T., Arai, S., and Nishida, A. Synlett 2004, 907
18. Nazare, M., Schneider, C., Lindenschmidt, A., and Will, D. W. Angew. Chem., Int. Ed. 2004, 43, 4526
19. Jia, Y. and Zhu, J. J. Org. Chem. 2006, 71, 7826
20. Leogane, O. and Lebel, H. Angew. Chem., Int. Ed. 2008, 47, 350
21. For selected examples of transition metal-catalyzed pyrrole synthesis, see
22. Dhawan, R. and Arndtsen, B. A. J. Am. Chem. Soc. 2004, 126, 468
23. Lu, Y. and Arndtsen, B. A. Angew. Chem., Int. Ed. 2008, 47, 5430
24. Crawley, M. L., Goljer, I., Jenkins, D. J., Mehlmann, J. F., Nogle, L., Dooley, R., and Mahaney, P. E. Org. Lett. 2006, 8, 5837
25. Kel'in, A. V., Sromek, A. W., and Gevorgyan, V. J. Am. Chem. Soc. 2001, 123, 2075
26. Gabriele, B., Salerno, G., and Fazio, A. J. Org. Chem. 2003, 68, 7853
27. For representative applications in medicinal chemistry, see
28. Lanter, J. C., Fiordeliso, J. J., Alford, V. C., Zhang, X., Wells, K. M., Russell, R. K., Allan, G. F., Lai, M.-T., Linton, O. L., Lundeen, S., and Sui, Z. Bioorg. Med. Chem. Lett. 2007, 17, 2545
29. Watterson, S. H., Murali Dhar, T. G., Ballentine, S. K., Shen, Z., Barrish, J. C., Cheney, D., Fleener, C. A., Rouleau, K. A., Townsend, R., Hollenbaugh, D. L., and Iwanowicz, E. J. Bioorg. Med. Chem. Lett. 2003, 13, 1273
30. Curtis, N. R., Kulagowski, J. J., Leeson, P. D., Ridgill, M. P., Emms, F., Freedman, S. B., Patel, S., and Patel, S. Bioorg. Med. Chem. Lett. 1999, 9, 585
31. Ujjainwalla, F. and Walsh, T. F. Tetrahedron Lett. 2001, 41, 6441 For recent representative examples of the Larock indole synthesis in total synthesis, see: Newhouse, T., Lewis, C. A., and Baran, P. S. J. Am. Chem. Soc. 2009, 131, 6360
32. Newhouse, T. and Baran, P. S. J. Am. Chem. Soc. 2008, 130, 10886
33. Newhouse, T., Lewis, C. A., Eastman, K. J., and Baran, P. S. J. Am. Chem. Soc. 2010, 132, 7119
34. Garfunkle, J., Kimball, F. S., Trzupek, J. D., Takizawa, S., Shimamura, H., Tomishima, M., and Boger, D. L. J. Am. Chem. Soc. 2009, 131, 16036
35. For a recent and comprehensive review of rhodium(III)-catalyzed formation of heterocycles via annulative processes with internal alkynes, see
36. Satoh, T. and Miura, M. Chem.-Eur. J. 2010, 16, 11212
37. Ueura, K., Satoh, T., and Miura, M. Org. Lett. 2007, 9, 1407
38. Ueura, K., Satoh, T., and Miura, M. J. Org. Chem. 2007, 72, 5362
39. Wurtz, S., Rakshit, S., Neumann, J. J., Droge, T., and Glorius, F. Angew. Chem., Int. Ed. 2008, 47, 7230
40. Stuart, D. R., Bertrand-Laperle, M., Burgess, K. M. N., and Fagnou, K. J. Am. Chem. Soc. 2008, 130, 16474
41. Shi, Z., Zhang, C., Li, S., Pan, D., Ding, S., Cui, Y., and Jiao, N. Angew. Chem., Int. Ed. 2009, 48, 4572
42. Bernini, R., Fabrizi, G., Sferrazza, A., and Cacchi, S. Angew. Chem., Int. Ed. 2009, 48, 8078
43. Tan, Y. and Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 3676
44. Chen, J., Song, G., Pan, C.-L., and Li, X. Org. Lett. 2010, 12, 5426
45. Houlden, C. E., Bailey, C. D., Ford, J. G., Gagné, M. R., Lloyd-Jones, G. C., and Booker-Milburn, K. I. J. Am. Chem. Soc. 2008, 130, 10066
46. During the preparation of this manuscript, a conceptually interesting approach employing allylic, and one example of vinylic, C-H bond functionalization in the formation of pyrroles was reported; see
47. Rakshit, S., Patureau, F. W., and Glorius, F. J. Am. Chem. Soc. 2010, 132, 9585
48. 2-mediated isoquinoline salt formation, see
49. Li, L., Brennessel, W. W., and Jones, W. D. J. Am. Chem. Soc. 2008, 130, 12414 For examples of isoquinoline synthesis employing catalytic 1 and 2, see: Guimond, N. and Fagnou, K. J. Am. Chem. Soc. 2009, 131, 12050
50. Fukutani, T., Umeda, N., Hirano, K., Satoh, T., and Miura, M. Chem. Commun. 2009, 5141
51. Guimond, N., Gouliaras, C., and Fagnou, K. J. Am. Chem. Soc. 2010, 132, 6908
52. Mochida, S., Umeda, N., Hirano, K., Satoh, T., and Miura, M. Chem. Lett. 2010, 39, 744
53. Hyster, T. K. and Rovis, T. J. Am. Chem. Soc. 2010, 132, 10565
54. Song, G., Chen, D., Pan, C.-L., Crabtree, R. H., and Li, X. J. Org. Chem. 2010, 75, 7487
55. Su, Y., Zhao, M., Han, K., Song, G., and Li, X. Org. Lett. 2010, 12, 5462
56. Umeda, N., Tsurugi, H., Satoh, T., and Miura, M. Angew. Chem., Int. Ed. 2008, 47, 4019
57. Morimoto, K., Hirano, K., Satoh, T., and Miura, M. Org. Lett. 2010, 12, 2068
58. Wang, F., Song, G., and Li, X. Org. Lett. 2010, 12, 5430
59. Schipper, D. J., Hutchinson, M., and Fagnou, K. J. Am. Chem. Soc. 2010, 132, 6910
60. For pioneering work employing catalytic copper and air as the terminal oxidant, see ref 9.
61. This aspect of the chemistry was identified in a Synfacts Highlight of our previously reported indole synthesis, ref 10b. Synfacts 2009, 3, 254.
62. Li, L., Brennessel, W. W., and Jones, W. D. Organometallics 2009, 28, 3492
63. Subsequent to its use in our indole forming reaction, catalyst 2 has been utilized in the synthesis of isoquinolines (ref 13b) and in the hydroarylation of unactivated alkynes (ref 16) by our group. This catalyst (2) will soon be commercially available from Strem Chemicals, Inc.
64. It should be noted that the reaction set-up is operationally very simple and that there is no need for special precautions to exclude atmospheric air or moisture.
65. Other solvents were tested in order to avoid solvolysis of the product with t -AmOH. However, slow reactions and lower yields of the desired product were observed.
66. See Supporting Information for further details.
67. Sausville, E. A., Zaharevitz, D., Gussio, R., Meijer, L., Louarn-Leost, M., Kunick, C., Schultz, R., Lahusen, T., Headlee, D., Stinson, S., Arbuck, S. G., and Senderowicz, A. Pharmacol. Ther. 1999, 82, 285
68. Zaharevitz, D., Gussio, R., Leost, M., Senderowicz, A., Lahusen, T., Kunick, C., Meijer, L., and Sausville, E. A. Cancer Res. 1999, 59, 2566
69. Schultz, C., Link, A., Leost, M., Zaharevitz, D., Gussio, R., Sausville, E. A., Meijer, L., and Kunick, C. J. Med. Chem. 1999, 42, 2909
70. Kunick, C., Schultz, C., Lemcke, T., Zaharevitz, D., Gussio, R., Jalluri, R. K., Sausville, E. A., Leost, M., and Meijer, L. Bioorg. Med. Chem. Lett. 2000, 10, 567
71. Reichwald, C., Shimony, O., Dunkel, U., Sacerdoti-Sierra, N., Jaffe, C. L., and Kunick, C. J. Med. Chem. 2008, 51, 659
72. Stukenbrock, H., Mussmann, R., Geese, M., Ferandin, Y., Lozach, O., Lemcke, T., Kegel, S., Lomow, A., Burk, U., Dohrmann, C., Meijer, L., Austen, M., and Kunick, C. J. Med. Chem. 2008, 51, 2196
73. For previous syntheses of paullone and its derivatives, see
74. Baudoin, O., Cesario, M., Guénard, D., and Guéritte, F. J. Org. Chem. 2002, 67, 1199
75. Bremner, J. B. and Sengpracha, W. Tetrahedron 2005, 61, 5489
76. Henry, N., Blu, J., Bénéteau, V., and Mérour, J.-Y. Synthesis 2006, 3895
77. Avila-Zárraga, J. G., Lujan-Montelongo, A., Covarrubias- Zúñiga, A., and Romero-Ortega, M. Tetrahedron Lett. 2006, 47, 7987
78. Joucla, L., Popowycz, F., Lozach, O., Meijer, L., and Joseph, B. Helv. Chem. Act. 2007, 90, 753
79. Tobisu, M., Fujihara, H., Koh, K., and Chatani, N. J. Org. Chem. 2010, 75, 4841
80. A Hammett correlation and an Arrehnius plot are also provided in the Supporting Information.
81. Ryabov, A. D., Sakodinskaya, I. K., and Yatsimirsky, A. K. J. Chem. Soc., Dalton Trans. 1985, 2629
82. Davies, D. L., Donald, S. M. A., and Macgregor, S. A. J. Am. Chem. Soc. 2005, 127, 13754
83. Davies, D. L., Donald, S. M. A., Al-Duaij, O., Macgregor, S. A., and Pölleth, M. J. Am. Chem. Soc. 2006, 128, 4210
84. For a historical perspective on the evolution of the CMD mechanism in the chemical literature, including examples involving cyclometalation reactions, see
85. Lapointe, D. and Fagnou, K. Chem. Lett. 2010, 39, 1118
86. See the Supporting Information for exact details of data collection for the kinetic experiments.
87. 2)]; see Supporting Information for more details.
88. The lines drawn in Figure 5 are done in order to guide the reader's eye and do not represent a mathematical correlation.
89. Steinhoff, B. A., Guzei, I. A., and Stahl, S. S. J. Am. Chem. Soc. 2004, 126, 11268
90. Schultz, M. J., Adler, R. S., Zierkiewicz, W., Privalov, T., and Sigman, M. S. J. Am. Chem. Soc. 2005, 127, 8499
91. Zuend, S. J. and Jacobsen, E. N. J. Am. Chem. Soc. 2007, 129, 15872
92. The greater formation of the side product in chlorinated solvents is attributed to the presence of small amounts of HCl due to decomposition of the solvent.
93. a > 1 provided 12 in similar yield with pivalic acid giving optimal results; see the Supporting Information for further details.
94. This is opposite to what was previously observed by Jones for the stoichiometric cyclorhodation of benzylimines; see ref 19.
95. A method involving syringe pump addition of the alkyne was explored but was complicated by the small scale of the reaction. Therefore, syringe pump addition was abandoned for the sequential addition protocol.
96. In the pyrrole forming reaction, a mixture of regioisomers in a 3.5:1 ratio is observed with the same selectivity as that observed in the indole-forming reaction.
97. Fensome, A. J. Med. Chem. 2005, 48, 5092
98. Reaxys search of compound 18e provided only one hit
99. Garrido, D. O. A., Buldain, G., Ojea, M. I., and Frydman, B. J. Org. Chem. 1988, 53, 403