PdII-catalysed C-H functionalisation of indoles and pyrroles assisted by the removable N-(2-pyridyl)sulfonyl group: C2-alkenylation and dehydrogenative homocoupling

Chemistry - A European Journal

Volumn 16, Issue 31, 2010, Pages 9676-9685

  García Rubia, Alfonso ^a   Urones, Beatriz ^a   Arrayás, Ramón Gómez ^a   Carretero, Juan Carlos ^a  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

Alkenylation; C H functionalization; Nitrogen heterocycles; Palladium; Protecting groups

Indexed keywords

ALKENYLATION; C-H FUNCTIONALIZATION; CATALYST SYSTEM; COMPETITIVE KINETICS; DESULFONYLATION; ELECTRON-DEFICIENT; ELECTROPHILIC AROMATIC SUBSTITUTIONS; FUNCTIONALISATION; GOOD YIELD; HOMOCOUPLING; ISOLATED YIELD; NITROGEN HETEROCYCLES; PALLADATION; PROTECTING GROUP; PYRIDYL; REGIOCONTROL; STARTING MATERIALS; SUBSTITUTED ALKENE; SULFONYL GROUPS;

CATALYSIS; ORGANIC POLYMERS; PALLADIUM; STYRENE;

OLEFINS;

EID: 77955837658     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201001126     Document Type: Article

References (129)

1. For recent reviews on direct C-H functionalisation, see: a) R. Jazzar, J. Hitce, A. Renaudat, J. Sofack-Kreutzer, O. Badouin, Chem. Eur. J. 2010, 16, 2654;
2. b) T. W. Lyons, M. Sandord, Chem. Rev. 2010, 110, 1147;
3. c) J. Roger, A. L. Gottumukkala, H. Doucet, ChemCatChem 2010, 2, 20;
4. d) D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 2010, 110, 624;
5. e) L. Ackermann, R. Vicente, A. R. Kapdi, Angew. Chem. 2009, 121, 9976;
6. Angew. Chem. Int. Ed. 2009, 48, 9792;
7. f) X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. 2009, 121, 5196;
8. Angew. Chem. Int. Ed. 2009, 48, 5094;
9. g) G. P. McGlacken, L. M. Bateman, Chem. Soc. Rev. 2009, 38, 2447;
10. h) O. Daugulis, H.-Q. Do, D. Shabashov, Acc. Chem. Res. 2009, 42, 1074;
11. i) R. Giri, B.-F. Shi, K. M. Engle, N. Maugel, J.-Q. Yu, Chem. Soc. Rev. 2009, 38, 3242;
12. j) M. Miura, T. Satoh in Modern Arylation Methods (Ed.: L. Ackermann), Wiley-VCH, Weinheim, 2009, pp. 335-362.
13. a) S. Murai, F. Kakiuchi, S. Sekine, Y. Tanaka, A. Kamatani, M. Sonoda, N. Chatani, Nature 1993, 366, 529.
14. See also: b) L. N. Lewis, J. F. Smith, J. Am. Chem. Soc. 1986, 108, 2728.
15. C. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura, Y. Fujiwara, Science 2000, 287, 1992.
16. For selected examples, see: a) M. Tobisu, N. Chatani, Org. Lett. 2009, 11, 3250;
17. b) H. Zhou, Y.-H. Xu, W.-J. Chung, T.-P. Loh, Angew. Chem. 2009, 121, 5459;
18. Angew. Chem. Int. Ed. 2009, 48, 5355;
19. c) G. Brasche, J. García-Fortanet, S. L. Buchwald, Org. Lett. 2008, 10, 2207;
20. d) O. Daugulis, V. G. Zaitsev, Angew. Chem. 2005, 117, 4114
21. Angew. Chem. Int. Ed. 2005, 44, 4046.
22. B. Xiao, Y. Fu, T.-J. Gong, J. J. Dai, J. Yi, L. Liu, J. Am. Chem. Soc. 2010, 132, 468.
23. a) C. E. Houlden, M. Hutchby, C. D. Bailey, J. G. Ford, S. N. G. Tyler, M. R. Gagné, G. C. Lloyd-Jones, K. I. Booker-Milburn, Angew. Chem. 2009, 121, 1862;
24. Angew. Chem. Int. Ed. 2009, 48, 1830;
25. (b) W. Rauf, A. L. Thompson, J. M. Brown, Chem. Commun. 2009, 3874;
26. (c) C. E. Houlden, C. D. Bailey, J. G. Ford, M. R. Gagné, G. C. Lloyd-Jones, K. I. Booker-Milburn, J. Am. Chem. Soc. 2008, 130, 10066.
27. X. Zhao, C. S. Yeung, V. M. Dong, J. Am. Chem. Soc. 2010, 132, 5837.
28. a) M. Yamashita, K. Hirano, T. Satoh, M. Miura, Org. Lett. 2009, 11, 2337;
29. (b) C. Wang, I. Piel, F. Glorius, J. Am. Chem. Soc. 2009, 131, 4194.
30. a) D. Zhao, W. Wang, F. Yang, J. Lan, L. Yang, G. Gao, J. You, Angew. Chem. 2009, 121, 3346;
31. Angew. Chem. Int. Ed. 2009, 48, 3296;
32. (b) S. H. Cho, S. J. Hwang, S. Chang, J. Am. Chem. Soc. 2008, 130, 9254;
33. (c) K. S. Kanyiva, Y. Nakao, T. Hiyama, Angew. Chem. 2007, 119, 9028;
34. Angew. Chem. Int. Ed. 2007, 46, 8872.
35. M. Tobisu, R. Nakamura, Y. Kita, N. Chatani, J. Am. Chem. Soc. 2009, 131, 3174.
36. a) T. A. Boebel, J. F. Hartwig, J. Am. Chem. Soc. 2008, 130, 7534;
37. (b) T. Ohmura, Y. Takasaki, H. Furukawa, M. Suginome, Angew. Chem. 2009, 121, 2408;
38. Angew. Chem. Int. Ed. 2009, 48, 2372.
39. See also: a) H. Ihara, M. Suginome, J. Am. Chem. Soc. 2009, 131, 7502;
40. (b) J. Xu, G. Cheng, D. Su, Y. Liu, X. Wang, Y. Hu, Chem. Eur. J. 2009, 15, 13105;
41. (c) S. J. Pastine, D. V. Gribkov, D. Sames, J. Am. Chem. Soc. 2006, 128, 14220.
42. For a recent review on the relevance and catalytic functionalisation of indoles, see: M. Bandini, A. Eichholzer, Angew. Chem. 2009, 121, 9786;
43. Angew. Chem. Int. Ed. 2009, 48, 9608.
44. For a recent review on the metal-catalysed direct arylation of indoles, see: L. Joucla, L. Djakovitch, Adv. Synth. Catal. 2009, 351, 673.
45. a) D. R. Stuart, K. Fagnou, Science 2007, 316, 1172;
46. (b) D. R. Stuart, E. Villemure, K. Fagnou, J. Am. Chem. Soc. 2007, 129, 12072.
47. For an intramolecular variation, see: c) T. A. Dwight, N. R. Rue, R. Charyk, R. Josselyn, B. DeBoef, Org. Lett. 2007, 9, 3137.
48. For a review on cross-dehydrogenative homocouplings, see: a) V. T. Trepohl, M. Oestreich in Modern Arylation Methods (Ed.: L. Ackermann), Wiley-VCH, Weinheim, 2009, p. 221;
49. for selected examples, see: b) H. Egami, T. Katsuki, J. Am. Chem. Soc. 2009, 131, 6082;
50. c) S. R. Whitfield, M. S. Sanford, J. Am. Chem. Soc. 2007, 129, 15142;
51. d) M. Takahashi, K. Masui, H. Sekiguchi, N. Kobayashi, A. Mori, M. Funhashi, N. Tamaoki, J. Am. Chem. Soc. 2006, 128, 10930.
52. a) M. d'Ischia, A. Napolitano, A. Pezzella, P. Meredith, T. Sarna, Angew. Chem. 2009, 121, 3972;
53. Angew. Chem. Int. Ed. 2009, 48, 3914;
54. b) U. Pindur, Y. S. Kim, F. Mehrabani, Curr. Med. Chem. 1999, 6, 2969;
55. c) G. W. Gribble, S. J. Berthel in Studies in Natural Product Chemistry, Vol.12 (Ed.: Attaur-Rahman), Elsevier, New York, 1993, p. 365.
56. Z. Liang, J. Zhao, Y. Zhang, J. Org. Chem. 2010, 75, 170.
57. For a recent review on the applications of derivatives of 2,2'-biindole as receptors in anion complexation and synthesis, see: P. A. Gale, Chem. Commun. 2008, 4525.
58. For C3-H alkenylation of indoles, see: a) H. Yu, Z. Yu, Angew. Chem. 2009, 121, 2973;
59. Angew. Chem. Int. Ed. 2009, 48, 2929;
60. b) T. Itahara, K. Kawasaki, F. Ouseto, Synthesis 1984, 236;
61. c) Y. Yokoyama, T. Matsumoto, Y. Murakami, J. Org. Chem. 1995, 60, 1486;
62. d) Y. Nakao, K. S. Kanyiva, S. Oda, T. Hiyama, J. Am. Chem. Soc. 2006, 128, 8146, and references [21a] and [21c].
63. For the intermolecular C2-H alkenylation of indoles, see: a) N. P. Grimster, C. Gauntlett, C. R. A. Godfrey, M. J. Gaunt, Angew. Chem. 2005, 117, 3185;
64. Angew. Chem. Int. Ed. 2005, 44, 3125;
65. b) E. Capito, J. M. Brown, A. Ricci, Chem. Commun. 2005, 1854;
66. c) A. Maehara, H. Tsurugi, T. Satoh, M. Miura, Org. Lett. 2008, 10, 1159.
67. For intramolecular PdII-catalysed C-H alkenylation of indoles, see: a) E. M. Ferreira, B. M. Stoltz, J. Am. Chem. Soc. 2003, 125, 9578;
68. b) G. Abbiati, E. M. Beccalli, G. Broggini, C. Zoni, J. Org. Chem. 2003, 68, 7625;
69. c) A. Kong, X. Han, X. Lu, Org. Lett. 2006, 8, 1339;
70. d) J. A. Schiffner, A. B. Machotta, M. Oestreich, Synlett 2008, 2271.
71. For selected recent examples of C-H alkenylation of other aromatic ring systems, see: a) D.-H. Wang, K. M. Engle, B.-F. Shi, J.-Q. Yu, Science 2010, 327, 315;
72. b) Y. Lu, D.-H. Wang, K. M. Engle, J.-Q. Yu, J. Am. Chem. Soc. 2010, 132, 5916;
73. c) S. Ueda, T. Okada, H. Nagasawa, Chem. Commun. 2010, 46, 2462;
74. d) D. Cheng, T. Gallager, Org. Lett. 2009, 11, 2639;
75. e) Y.-H. Zhang, B.-F. Shi, J.-Q. Yu, J. Am. Chem. Soc. 2009, 131, 5072;
76. f) J.-J. Li, T.-S. Mei, J.-Q. Yu, Angew. Chem. 2008, 120, 6552;
77. Angew. Chem. Int. Ed. 2008, 47, 6452;
78. g) Y. Nakao, K. S. Kanyiva, T. Hiyama, J. Am. Chem. Soc. 2008, 130, 2448;
79. h) G. Cai, Y. Fu, Y. Li, X. Wan, Z. Shi, J. Am. Chem. Soc. 2007, 129, 7666, and reference [6c];
80. see also: i) M. Wasa, K. M. Engle, Y.-Q. Yu, J. Am. Chem. Soc. 2010, 132, 3680.
81. For recent applications of the 2-pyridylsulfonyl group in metal-catalysed reactions of N-sulfonyl imines, see: a) J. Esquivias, R. Gómez Arrayás, J. C. Carretero, Angew. Chem. 2007, 119, 9417;
82. Angew. Chem. Int. Ed. 2007, 46, 9257;
83. b) J. Hernández-Toribio, R. Gómez Arrayás, J. C. Carretero, J. Am. Chem. Soc. 2008, 130, 16150;
84. c) S. Nakamura, H. Nakashima, H. Sugimoto, M. Hattori, N. Shibata, T. Toru, Chem. Eur. J. 2008, 14, 2145;
85. d) S. Nakamura, H. Nakashima, A. Yamamura, N. Shibata, T. Toru, Adv. Synth. Catal. 2008, 350, 1209;
86. e) S. Nakamura, Y. Sakurai, H. Nakashima, N. Shibata, T. Toru, Synlett 2009, 1639;
87. f) J. Esquivias, R. Gómez Arrayás, J. C. Carretero, Synthesis 2009, 113.
88. For vinyl sulfones, see: g) T. Llamas, R. Gómez Arrayás, J. C. Carretero, Angew. Chem. 2007, 119, 3393;
89. Angew. Chem. Int. Ed. 2007, 46, 3329;
90. h) J.-N. Desrosiers, W. S. Bechara, A. B. Charette, Org. Lett. 2008, 10, 2315;
91. i) P. H. Bos, A. J. Minnaard, B. L. Feringa, Org. Lett. 2008, 10, 4219;
92. j) P. Mauleón, I. Alonso, M. Rodríguez Rivero, J. C. Carretero, J. Org. Chem. 2007, 72, 9924.
93. For a preliminary communication of this work, see: A. García- Rubia, R. Gómez Arrayás, J. C. Carretero, Angew. Chem. 2009, 121, 6633;
94. Angew. Chem. Int. Ed. 2009, 48, 6511.
95. T. Itahara, M. Ikeda, T. Sakakibara, J. Chem. Soc. Perkin Trans. 1 1983, 1361.
96. 2 as the sacrificial oxidant led to product 17 in 70% conversion. See the Supporting Information for catalyst system optimisation studies.
97. Y. Nakao, N. Nashihara, K. S. Kanyiva, T. Hiyama, J. Am. Chem. Soc. 2008, 130, 16170.
98. 1H NMR spectroscopy, mainly by NOE experiments, see the Supporting Information for details.
99. For PdII-catalysed C-H alkenylation of pyrroles, see: a) E. M. Beck, N. P. Grimster, R. Hatley, M. J. Gaunt, J. Am. Chem. Soc. 2006, 128, 2528;
100. b) E. M. Beck, R. Hatley, M. J. Gaunt, Angew. Chem. 2008, 120, 3046;
101. Angew. Chem. Int. Ed. 2008, 47, 3004.
102. For C2-H arylation of 3-substituted indoles, see: a) M. Miyasaka, A. Fukushima, T. Satoh, K. Hirano, M. Miura, Chem. Eur. J. 2009, 15, 3674;
103. b) B. B. Touré, B. S. Lane, D. Sames, Org. Lett. 2006, 8, 1979.
104. See, for instance: L. Djakovitch, V. Dufaud, R. Zaidi, Adv. Synth. Catal. 2006, 348, 715.
105. For an example of the directed C7-H alkenylation of indoles, see: G. Fanton, N. M. Coles, A. R. Cowley, J. P. Flemming, J. M. Brown, Heterocycles 2010, 80, 895.
106. See, for instance: a) P. S. Baran, J. M. Richter, D. W. Lin, Angew. Chem. 2005, 117, 615;
107. Angew. Chem. Int. Ed. 2005, 44, 609;
108. b) N. K. Garg, D. D. Caspii, B. M. Stoltz, J. Am. Chem. Soc. 2005, 127, 5970;
109. c) O. V. Larionov, A. de Meijere, Angew. Chem. 2005, 117, 5809;
110. Angew. Chem. Int. Ed. 2005, 44, 5664.
111. E Ar mechanism and/or the presence of an additional basic N atom that could bind to Pd and inhibit catalysis
112. Compounds 87-94 are known. See the Supporting Information for details.
113. 2=tBu). On the other hand, C2 palladation of indoles containing a strongly directing group with stoichiometric amounts of the palladium source have also been reported, see: a) S. Tollari, F. Demartin, S Cenini, G. Palmisano, P. Raimondi, J. Organomet. Chem. 1997 527 93
114. (b) M. Nonoyama, K. Nakajima, Polyhedron 1998, 18, 533. See also reference [21b].
115. 3CN, 80°C), only the more electron-rich substrate 72 gave olefination product 77, while the electron-poor pyrrole 73 remained unaltered
116. 2Cl/NaH (55% over the last two steps). Attempts to effect direct bromo/lithium exchange from 2-bromo-N-(2-pyridyl) sulfonyl pyrrole resulted in competitive deprotonation at the pyridyl ring. See the Supporting Information for experimental details
117. A similar kinetic isotope effect has been observed in PdII-catalysed C2-H arylation of indoles: a) B. S. Lane, M. A. Brown, D. Sames, J. Am. Chem. Soc. 2005, 127, 8050.
118. For related results in other aromatic systems, see: b) J.-J. Li, R. Giri, J.-Q. Yu, Tetrahedron 2008, 64, 6979;
119. c) S. Chuprakov, N. Chernyak, A. S. Dudnik, V. Gevorgyan, Org. Lett. 2007, 9, 2333;
120. for mechanistic studies supporting a concerted metallation/proton abstraction in Pd-catalysed arylations, see, for instance: d) S. Pascual, P. de Mendoza, A. A. C. Braga, F. Maseras, A. M. Echavarren, Tetrahedron 2008, 64, 6021;
121. e) D. García-Cuadrado, P. de Mendoza, A. A. C. Braga, F. Maseras, A. M. Echavarren, J. Am. Chem. Soc. 2007, 129, 6880;
122. f) S. I. Gorelsky, D. Lapointe, K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848;
123. g) Z. Shi, B. Li, X. Wan, J. Cheng, Z. Fang, C. Qin, Y. Wang, Angew. Chem. 2007, 119, 5650;
124. Angew. Chem. Int. Ed. 2007, 46, 5554; see also reference [23i].
125. Attempts to access such palladacycles by oxidative addition to 2- bromo-N-(2-pyridyl)sulfonyl indole resulted in the formation of complex mixtures.
126. CCDC-736591 [unit cell parameters: a=8.4276(2), b=11.8616(2), c=12.3533(3) Å, α=105.9180(10), β=106.289(2), γ=91.296(2)°, space group P1̄ ] contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data- request/cif.
127. 2-promoted intramolecular 2,2'-oxidative coupling of N,N'-carbonyl indole, see: J. Bergman, N. Eklund, Tetrahedron 1980, 36, 1439.
128. 2.
129. 3 CN or tBuOH, resulted in conversions lower than 20%. Propionic acid was similarly effective, but not TFA.