Investigation of the mechanism of C(sp3)-H bond cleavage in Pd(0)-catalyzed intramolecular alkane arylation adjacent to amides and sulfonamides

Journal of the American Chemical Society

Volumn 132, Issue 31, 2010, Pages 10692-10705

  Rousseaux, Sophie ^a   Gorelsky, Serge I ^a   Chung, Benjamin K W ^a   Fagnou, Keith ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ARYLATIONS; CATALYTIC ACTIVITY; CONCENTRATION OF; DFT CALCULATION; GOOD YIELD; H-BONDS; KINETIC ISOTOPE EFFECTS; KINETIC STUDY; LEWIS BASICITY; LONE PAIR; METALATIONS; NITROGEN ATOM; REACTION INTERMEDIATE; REACTION MECHANISM; TRANSITION STATE;

AMIDES; AROMATIC COMPOUNDS; CHEMICAL REACTIONS; ISOTOPES; PALLADIUM; PALLADIUM COMPOUNDS; PARAFFINS; PHOSPHORUS COMPOUNDS; REACTION RATES; SULFUR COMPOUNDS;

REACTION INTERMEDIATES;

ALKANE DERIVATIVE; AMIDE; LEAD; LEWIS BASE; NITROGEN; SULFONAMIDE;

ARTICLE; ARYLATION; CATALYSIS; CHEMICAL REACTION; HYDROGEN BOND; STOICHIOMETRY;

ALKANES; AMIDES; CATALYSIS; CRYSTALLOGRAPHY, X-RAY; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; PALLADIUM; STEREOISOMERISM;

EID: 77955405522     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja103081n     Document Type: Article

References (234)

1. 3)-H bonds for C-C bond formation
2. Periana, R. A., Mironov, O., Taube, D., Bhalla, G., and Jones, C. J. Science 2003, 301, 814
3. Zerella, M., Mukhopadhyay, S., and Bell, A. T. Chem. Commun. 2004, 1948
4. Chen, X., Goodhue, C. E., and Yu, J.-Q. J. Am. Chem. Soc. 2006, 128, 12634
5. Giri, R., Maugel, N., Li, J.-J., Wang, D.-H., Breazzano, S. P., Saunders, L. B., and Yu, J.-Q. J. Am. Chem. Soc. 2007, 129, 3510
6. Wang, D.-H., Wasa, M., Giri, R., and Yu, J.-Q. J. Am. Chem. Soc. 2008, 130, 7190
7. Shi, B.-F., Maugel, N., Zhang, Y.-H., and Yu, J.-Q. Angew. Chem., Int. Ed. 2008, 47, 4882
8. Lin, S., Song, C.-X., Cai, G.-X., Wang, W.-H., and Shi, Z.-J. J. Am. Chem. Soc. 2008, 130, 12901
9. Young, A. J. and White, M. C. J. Am. Chem. Soc. 2008, 130, 14090
10. Liégault, B. and Fagnou, K. Organometallics 2008, 27, 4841
11. Wasa, M., Engle, K. M., and Yu, J.-Q. J. Am. Chem. Soc. 2010, 132, 3680
12. 3)-H bonds for C-C bond formation
13. Catellani, M., Motti, E., and Ghelli, S. Chem. Commun. 2000, 2003
14. Zaitsev, V. D., Shabashov, D., and Daugulis, O. J. Am. Chem. Soc. 2005, 127, 13154
15. Kalyani, D., Deprez, N. R., Desai, L. V., and Sanford, M. S. J. Am. Chem. Soc. 2005, 127, 7330
16. Shabashov, D. and Daugulis, O. Org. Lett. 2005, 7, 3657
17. Reddy, B. V. S., Reddy, L. R., and Corey, E. J. Org. Lett. 2006, 8, 3391
18. Deprez, N. R. and Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 11234
19. Shabashov, D. and Daugulis, O. J. Am. Chem. Soc. 2010, 132, 3965 See also ref 1d.
20. 3)-H bonds for C-C bond formation
21. Dyker, G. Angew. Chem., Int. Ed. Engl. 1992, 31, 1023
22. Dyker, G. J. Org. Chem. 1993, 58, 6426
23. Dyker, G. Angew. Chem., Int. Ed. Engl. 1994, 33, 103
24. Baudoin, O., Herrbach, A., and Guéritte, F. Angew. Chem., Int. Ed. 2003, 42, 5736
25. Zhao, J., Campo, M., and Larock, R. C. Angew. Chem., Int. Ed. 2005, 44, 1873
26. Barder, T. E., Walker, S. D., Martinelli, J. R., and Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4685
27. Ren, H. and Knochel, P. Angew. Chem., Int. Ed. 2006, 45, 3462
28. Dong, C.-G. and Hu, Q.-S. Angew. Chem., Int. Ed. 2006, 45, 2289
29. Dong, C.-G. and Hu, Q.-S. Org. Lett. 2006, 8, 5057
30. Lafrance, M., Gorelsky, S. I., and Fagnou, K. J. Am. Chem. Soc. 2007, 129, 14570
31. Niwa, T., Yorimitsu, H., and Oshima, K. Org. Lett. 2007, 9, 2373
32. Ren, H., Li, Z., and Knochel, P. Chem. Asian J. 2007, 2, 416
33. Hitce, J., Retailleau, P., and Baudoin, O. Chem.-Eur. J. 2007, 13, 792
34. Dong, C.-G., Yeung, P., and Hu, Q.-S. Org. Lett. 2007, 9, 363
35. Liron, F. and Knochel, P. Tetrahedron Lett. 2007, 48, 4943
36. Campeau, L.-C., Schipper, D. J., and Fagnou, K. J. Am. Chem. Soc. 2008, 130, 3266
37. Mousseau, J. J., Larivée, A., and Charette, A. B. Org. Lett. 2008, 10, 1641
38. Niwa, T., Yorimitsu, H., and Oshima, K. Org. Lett. 2008, 10, 4689
39. Watanabe, T., Oishi, S., Fujii, N., and Ohno, H. Org. Lett. 2008, 10, 1759
40. Kim, H. S., Gowrisankar, S., Kim, S. H., and Kim, J. N. Tetrahedron Lett. 2008, 49, 3858
41. Dong, C.-G. and Hu, Q.-S. Tetrahedron 2008, 64, 2537
42. Chaumontet, M., Piccardi, R., Audic, N., Hitce, J., Peglion, J.-L., Clot, E., and Baudoin, O. J. Am. Chem. Soc. 2008, 130, 15157
43. Salcedo, A., Neuville, L., and Zhu, J. J. Org. Chem. 2008, 73, 3600
44. Schipper, D. J., Campeau, L.-C., and Fagnou, K. Tetrahedron 2009, 65, 3155
45. Wasa, M., Engle, K. M., and Yu, J.-Q. J. Am. Chem. Soc. 2009, 131, 9886
46. Chaumontet, M., Piccardi, R., and Baudoin, O. Angew. Chem., Int. Ed. 2009, 48, 179
47. Chaumontet, M., Retailleau, P., and Baudoin, O. J. Org. Chem. 2009, 74, 1774
48. Liu, T.-P., Xing, C.-H., and Hu, Q.-S. Angew. Chem., Int. Ed. 2010, 49, 2909
49. 3)-H bonds for C-C bond formation: Ruthenium Pastine, S. J., Gribkov, D. V., and Sames, D. J. Am. Chem. Soc. 2006, 128, 14220
50. Jovel, I., Prateeptongkum, S., Jackstell, R., Vogl, N., Weckbecker, C., and Beller, M. Chem. Commun. 2010, 1956 Rhodium Ishii, Y., Chatani, N., Kakiuchi, F., and Murai, S. Organometallics 1997, 16, 3615
51. Chatani, N., Asaumi, T., Ikeda, T., Yorimitsu, S., Ishii, Y., Kakiuchi, F., and Murai, S. J. Am. Chem. Soc. 2000, 122, 12882
52. Kim, M., Kwak, J., and Chang, S. Angew. Chem., Int. Ed. 2009, 48, 8935
53. Iridium DeBoef, B., Pastine, S. J., and Sames, D. J. Am. Chem. Soc. 2004, 126, 6556
54. Tsuchikama, K., Kasagawa, M., Endo, K., and Shibata, T. Org. Lett. 2009, 11, 1821
55. Guo, Y., Zhao, X., Zhang, D., and Murahashi, S.-I. Angew. Chem., Int. Ed. 2009, 48, 2047
56. Bexrud, J. A., Eisenberger, P., Leitch, D. C., Payne, P. R., and Schafer, L. L. J. Am. Chem. Soc. 2009, 131, 2116
57. Kubiak, R., Prochnow, I., and Doye, S. Angew. Chem., Int. Ed. 2010, 49, 2626 Tantalum Herzon, S. B. and Hartwig, J. F. J. Am. Chem. Soc. 2007, 129, 6690
58. Eisenberger, P., Ayinla, R. O., Lauzon, J. M. P., and Schafer, L. L. Angew. Chem., Int. Ed. 2009, 48, 8361
59. Vadola, P. A. and Sames, D. J. Am. Chem. Soc. 2009, 131, 16525
60. 3)-H bonds for C-X bond formation
61. Kitajima, N. and Schwartz, J. J. Am. Chem. Soc. 1984, 106, 2220
62. Olah, G. A., Gupta, B., Farina, M., Felberg, J. D., Ip, W. M., Husain, A., Karpeles, R., Lammertsma, K., Melhotra, A. K., and Trivedi, N. J. J. Am. Chem. Soc. 1985, 107, 7097
63. Horváth, I. T., Cook, R. A., Millar, J. M., and Kiss, G. Organometallics 1993, 12, 8
64. Giri, R., Chen, X., and Yu, J.-Q. Angew. Chem., Int. Ed. 2005, 44, 2112
65. Giri, R., Chen, X., Hao, X.-S., Li, J.-J., Liang, J., Fan, Z.-P., and Yu, J.-Q. Tetrahedron: Asymmetry 2005, 16, 3502
66. Hull, K. L., Anani, W. Q., and Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 7134
67. Giri, R., Wasa, M., Breazzano, S. P., and Yu, J.-Q. Org. Lett. 2006, 8, 5685
68. 3)-H bonds for C-B bond formation
69. Chen, H. and Hartwig, J. F. Angew. Chem., Int. Ed. 1999, 38, 3391
70. Chen, H., Schlecht, S., Semple, T. C., and Hartwig, J. F. Science 2000, 287, 1995
71. Shimada, S., Batsanov, A. S., Howard, J. A. K., and Marder, T. B. Angew. Chem., Int. Ed. 2001, 40, 2168
72. Lawrence, J. D., Takahashi, M., Bae, C., and Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 15334
73. Murphy, J. M., Lawrence, J. D., Kawamura, K., Incarvito, C., and Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 13684
74. Olsson, V. J. and Szabó, K. J. Angew. Chem., Int. Ed. 2007, 46, 6891
75. 3)-H bond for C-Si bond formation
76. Kakiuchi, F., Tsuchiya, K., Matsumoto, M., Mizushima, E., and Chatani, N. J. Am. Chem. Soc. 2004, 126, 12792
77. 3)-H bonds for C-O bond formation
78. Heumann, A., Reglier, M., and Waegell, B. Angew. Chem., Int. Ed. Engl. 1982, 21, 366
79. Heumann, A. and Akermark, B. Angew. Chem., Int. Ed. Engl. 1984, 96, 443
80. McMurry, J. E. and Koovsky, P. Tetrahedron Lett. 1984, 25, 4187
81. Periana, R. A., Taube, D. J., Gamble, S., Taube, H., Satoh, T., and Fujii, H. Science 1998, 280, 560
82. Lin, M., Shen, C., Garcia-Zayas, E. A., and Sen, A. J. Am. Chem. Soc. 2001, 123, 1000
83. Dangel, B. D., Johnson, J. A., and Sames, D. J. Am. Chem. Soc. 2001, 123, 8149
84. Muehlhofer, M., Strassner, T., and Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1745
85. Dick, A. R., Hull, K. L., and Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 2300
86. Jones, C. J., Taube, D., Ziatdinov, V. R., Periana, R. A., Nielsen, R. J., Oxgaard, J., and Goddard, W. A., III. Angew. Chem., Int. Ed. 2004, 43, 4626
87. Desai, L. V., Hull, K. L., and Sanford, M. S. J. Am. Chem. Soc. 2004, 126, 9542
88. Chen, M. S. and White, M. C. J. Am. Chem. Soc. 2004, 126, 1346
89. Giri, R., Liang, J., Lei, J.-G., Li, J.-J., Wang, D.-H., Chen, X., Naggar, I. C., Guo, C., Foxman, B. M., and Yu, J.-Q. Angew. Chem., Int. Ed. 2005, 44, 7420
90. Chen, M. S., Prabagaran, N., Labenz, N. A., and White, M. C. J. Am. Chem. Soc. 2005, 127, 6970
91. Fraunhoffer, K. J., Bachovchin, D. A., and White, M. C. Org. Lett. 2005, 7, 223
92. Desai, L. V., Malik, H. A., and Sanford, M. S. J. Am. Chem. Soc. 2006, 8, 1141
93. Wang, D.-H., Hao, X.-S., Wu, D.-F., and Yu, J.-Q. Org. Lett. 2006, 8, 3387
94. Lee, J. M. and Chang, S. Tetrahedron Lett. 2006, 47, 1375
95. Fraunhoffer, K. J., Prabagaran, N., Sirois, L. E., and White, M. C. J. Am. Chem. Soc. 2006, 128, 9032
96. Delcamp, J. H. and White, M. C. J. Am. Chem. Soc. 2006, 128, 15076
97. Zhang, J., Khaskin, E., Anderson, N. P., Zavalij, P. Y., and Vedernikov, A. N. Chem. Commun. 2008, 3625
98. Covell, D. J. and White, M. C. Angew. Chem., Int. Ed. 2008, 47, 6448 See also ref 2e.
99. 3)-H bonds for C-N bond formation
100. Espino, C. G., When, P. M., Chow, J., and Du Bois, J. J. Am. Chem. Soc. 2001, 123, 6935
101. Fraunhoffer, K. J. and White, M. C. J. Am. Chem. Soc. 2007, 129, 7274
102. Du, H., Yuan, W., Zhao, B., and Shi, Y. J. Am. Chem. Soc. 2007, 129, 7496
103. Wasa, M. and Yu, J.-Q. J. Am. Chem. Soc. 2008, 130, 14058
104. Reed, S. A. and White, M. C. J. Am. Chem. Soc. 2008, 130, 3316
105. Liu, G., Yin, G., and Wu, L. Angew. Chem., Int. Ed. 2008, 47, 4733
106. Wang, B., Du, H., and Shi, Y. Angew. Chem., Int. Ed. 2008, 47, 8224
107. Du, H., Zhao, B., and Shi, Y. J. Am. Chem. Soc. 2008, 130, 8590
108. Wu, L., Qiu, S., and Liu, G. Org. Lett. 2009, 11, 2707
109. Neumann, J. J., Rakshit, S., Dröge, T., and Glorius, F. Angew. Chem., Int. Ed. 2009, 48, 6892
110. Reed, S. A., Mazzotti, A. R., and White, M. C. J. Am. Chem. Soc. 2009, 131, 11701
111. Rice, G. T. and White, M. C. J. Am. Chem. Soc. 2009, 131, 11707
112. 3)-H bonds for C-S bond formation
113. Mukhopadhyay, S. and Bell, A. T. Angew. Chem., Int. Ed. 2003, 42, 2990
114. 3)-H bonds
115. Miura, M. and Nomura, M. Top. Curr. Chem. 2002, 219, 212
116. Lloyd-Jones, G. C. Angew. Chem., Int. Ed. 2002, 41, 953
117. Culkin, D. A. and Hartwig, J. F. Acc. Chem. Res. 2003, 36, 234
118. Bellina, F. and Rossi, R. Chem. Rev. 2009, 110, 1082
119. Johansson, C. C. C. and Colacot, T. J. Angew. Chem., Int. Ed. 2010, 49, 676
120. 3)-H bonds
121. Yu, J.-Q., Giri, R., and Chen, X. Org. Biomol. Chem. 2006, 4, 4041
122. Campos, K. R. Chem. Soc. Rev. 2007, 36, 1069
123. Jazzar, R., Hitce, J., Renaudat, A., Sofack-Kreutzer, J., and Baudoin, O. Chem.-Eur. J. 2010, 16, 2654. See also ref 11
124. For selected general reviews on catalytic transformations at C-H bonds for the formation of C-C and C-X bonds
125. Kakiuchi, F. and Chatani, N. Adv. Synth. Catal. 2003, 345, 1077
126. Handbook of C-H Transformations; Dyker, G., Ed.; Wiley-VCH: Weinheim, 2005.
127. Godula, K. and Sames, D. Science 2006, 312, 67
128. Dick, A. R. and Sanford, M. S. Tetrahedron 2006, 62, 2439
129. Thansandote, P. and Lautens, M. Chem.-Eur. J. 2009, 15, 5974
130. Zhang, M. Adv. Synth. Catal. 2009, 351, 2243
131. Lyons, T. W. and Sanford, M. S. Chem. Rev. 2010, 110, 1147
132. For selected reviews on catalytic transformations at C-H bonds for the formation of C-C bonds
133. Dyker, G. Angew. Chem., Int. Ed. 1999, 38, 1698
134. Ritleng, V., Sirlin, C., and Pfeffer, M. Chem. Rev. 2002, 102, 1731
135. Goj, L. A. and Gunnoe, T. B. Curr. Org. Chem. 2005, 9, 671
136. Daugulis, O., Zaitsev, V. G., Shabashov, D., Pham, Q. N., and Lazareva, A. Synlett 2006, 3382
137. Alberico, D., Scott, M. E., and Lautens, M. Chem. Rev. 2007, 107, 174
138. Seregin, I. V. and Gevorgyan, V. Chem. Soc. Rev. 2007, 36, 1173
139. Satoh, T. and Miura, M. Chem. Lett. 2007, 36, 200
140. Campeau, L.-C., Stuart, D. R., and Fagnou, K. Aldrich. Chim. Acta 2007, 40, 35
141. Chen, X., Engle, K. M., Wang, D.-H., and Yu, J.-Q. Angew. Chem., Int. Ed. 2009, 48, 5094
142. Daugulis, O., Do, H.-Q., and Shabashov, D. Acc. Chem. Res. 2009, 42, 1074
143. McGlacken, G. P. and Bateman, L. M. Chem. Soc. Rev. 2009, 38, 2447
144. 2)-H bonds
145. Campeau, L.-C. and Fagnou, K. Chem. Commun. 2006, 1253
146. Li, B.-J., Yang, S.-D., and Shi, Z.-J. Synlett 2008, 949
147. 2)-H bonds
148. Kakiuchi, F. and Murai, S. Acc. Chem. Res. 2002, 35, 826
149. Lewis, J. C., Bergman, R. G., and Ellman, J. A. Acc. Chem. Res. 2008, 41, 1013
150. Colby, D. A., Bergman, R. G., and Ellman, J. A. Chem. Rev. 2010, 110, 624
151. 3)-H bonds involving an outer-sphere mechanism
152. Davies, H. M. L. and Beckwith, R. E. J. Chem. Rev. 2003, 103, 2861
153. Davies, H. M. L. and Loe, O. Synthesis 2004, 2595
154. Davies, H. M. L. and Manning, J. R. Nature 2008, 451, 417
155. Díaz-Requejo, M. M. and Pérez, P. J. Chem. Rev. 2008, 108, 3379
156. Zalatan, D. N. and Du Bois, J. Top. Curr. Chem. 2009, 1436
157. Collet, F., Dodd, R. H., and Dauban, P. Chem. Commun. 2009, 5061
158. Doyle, M. P., Duffy, R., Ratnikov, M., and Zhou, L. Chem. Rev. 2010, 110, 704 See also ref 13d.
159. 3)-H bonds
160. Shilov, A. E. and Shteinman, A. A. Coord. Chem. Rev. 1977, 24, 97 and references therein
161. Labinger, J. A. J. Mol. Catal. A: Chem. 2004, 220, 27 and references therein
162. 3)-H bonds
163. Ryabov, A. D. Chem. Rev. 1990, 90, 403
164. Shilov, A. E. and Shulpin, G. B. Chem. Rev. 1997, 97, 2879
165. Stahl, S. S., Labinger, J. A., and Bercaw, J. E. Angew. Chem., Int. Ed. 1998, 37, 2180
166. Crabtree, R. H. J. Chem. Soc., Dalton Trans. 2001, 2437
167. Labinger, J. A. and Bercaw, J. E. Nature 2002, 417, 507
168. Crabtree, R. H. J. Organomet. Chem. 2004, 689, 4083
169. Lersch, M. and Tilset, M. Chem. Rev. 2005, 105, 2471
170. For selected reviews
171. Biswas, B., Sugimoto, M., and Sakaki, S. Organometallics 2000, 19, 3895
172. Pascual, S., de Mendoza, P., and Echavarren, A. M. Org. Biomol. Chem. 2007, 5, 2727
173. Boutadla, Y., Davies, D. L., Macgregor, S. A., and Poblador-Bahamonde, A. I. Dalton Trans. 2009, 5820
174. Balcells, D., Clot, E., and Eisenstein, O. Chem. Rev. 2010, 110, 749
175. 2)-H bonds
176. Mota, A. J., Dedieu, A., Bour, C., and Suffert, J. J. Am. Chem. Soc. 2005, 127, 7171
177. Davies, D. L., Donald, S. M. A., and Macgregor, S. A. J. Am. Chem. Soc. 2005, 127, 13754
178. García-Cuadrado, D., Braga, A. A. C., Maseras, F., and Echavarren, A. M. J. Am. Chem. Soc. 2006, 128, 1066
179. Davies, D. L., Donald, S. M. A., Al-Duaij, O., Macgregor, S. A., and Pölleth, M. J. Am. Chem. Soc. 2006, 128, 4210
180. Lafrance, M., Rowley, C. N., Woo, T. K., and Fagnou, K. J. Am. Chem. Soc. 2006, 128, 8754
181. Lafrance, M. and Fagnou, K. J. Am. Chem. Soc. 2006, 128, 16496
182. García-Cuadrado, D., de Mendoza, P., Braga, A. A. C., Maseras, F., and Echavarren, A. M. J. Am. Chem. Soc. 2007, 129, 6880
183. Ackermann, L., Vicente, R., and Althammer, A. Org. Lett. 2008, 10, 2299
184. Caron, L., Campeau, L.-C., and Fagnou, K. Org. Lett. 2008, 10, 4533
185. Gorelsky, S. I., Lapointe, D., and Fagnou, K. J. Am. Chem. Soc. 2008, 130, 10848
186. Lafrance, M., Lapointe, D., and Fagnou, K. Tetrahedron 2008, 64, 6015
187. Pascual, S., de Mendoza, P., Braga, A. A. C., Maseras, F., and Echavarren, A. M. Tetrahedron 2008, 64, 6021
188. Özdemir, I., Demir, S., Çetinkaya, B., Gourlaouen, C., Maseras, F., Bruneau, C., and Dixneuf, P. H. J. Am. Chem. Soc. 2008, 130, 1156
189. Liégault, B., Lapointe, D., Caron, L., Vlassova, A., and Fagnou, K. J. Org. Chem. 2009, 74, 1826
190. Liégault, B., Petrov, I., Gorelsky, S. I., and Fagnou, K. J. Org. Chem. 2010, 75, 1047
191. For a review on agostic interactions in transition metal compounds
192. Brookhart, M., Green, M. L. H., and Parkin, G. Proc. Natl. Acad. Sci. U.S.A. 2007, 104, 6908
193. For examples utilizing Dykers methodology
194. Kim, H. S., Gowrisankar, S., Kim, S. H., and Kim, J. N. Tetrahedron Lett. 2008, 49, 3858
195. Suau, R., López-Romero, J. M., and Rico, R. Tetrahedron Lett. 1996, 37, 9357
196. 3)-H bonds adjacent to nitrogen for the formation of C-C bonds, see ref 4 a,d,f. For metal-catalyzed transformations proceeding via a radical mechanism
197. Baslé, O. and Li, C.-J. Org. Lett. 2008, 10, 3661
198. Yoshikai, N., Mieczkowski, A., Matsumoto, A., Ilies, L., and Nakamura, E. J. Am. Chem. Soc. 2010, 132, 5568
199. For a review:
200. Murahashi, S.-I. and Takaya, H. Acc. Chem. Res. 2000, 33, 225
201. This pathway is indeed a well-known mechanism for the generation of Pd(0) from the reaction of Pd(II) precatalysts with triethylamine in other traditional cross-coupling reactions. As well, the undesired dehalogenation of aryl halides via this mechanism has been previously documented in the development of palladium-catalyzed aryl amination reactions as well as other palladium-catalyzed cross-coupling processes. See
202. Brenda, M., Knebelkamp, A., Greiner, A., and Heitz, W. Synlett 1991, 809
203. Guram, A. S., Rennels, R. A., and Buchwald, S. L. Angew. Chem., Int. Ed. Engl. 1995, 34, 1348
204. Hartwig, J. F., Richards, S., Barañano, D., and Paul, F. J. Am. Chem. Soc. 1996, 118, 3626
205. A signal (s) at 45 ppm was observed for the corresponding N -(2-bromobenzyl)- N -dimethylamine derived complex, see
206. Bedford, R. B. and Cazin, C. S. J. Organometallics 2003, 22, 987
207. Under reaction conditions previously reported by our group for alkane arylation of these types of ethers, substrate 3 is converted to 2,2-dialkyldihydrobenzofuran 5 in 97% yield and 6 is converted to 7 in 91% yield (see ref 3j).
208. The nature of the intrinsic difference in reactivity of pivalate vs acetate additives remains ellusive at this time. The significant decrease in yield when acetic acid is used instead of pivalic acid as an additive in Pd(0)-catalyzed transformations at C-H bonds has been previously observed (see refs 3j and 21f,k). Efforts are underway to further understand these observations.
209. 1H NMR time scale.
210. The larger KIE value for intermolecular vs intramolecular competitions is atypical and is not fully understood at this time although errors on side-by-side intermolecular competitions are intrinsically larger due to the nature of the experiment. In any case, the conclusion of a rate-limiting C-H bond cleaving event remains.
211. See Supporting Information for further details on kinetic experiments.
212. For selected mechanistic studies on oxidative addition of Pd(0) to aryl halides
213. Amatore, C. and Pflüger, F. Organometallics 1990, 9, 2276
214. Hartwig, J. F. and Frédéric, P. J. Am. Chem. Soc. 1995, 117, 5373
215. Amatore, C., Bucaille, A., Fuxa, A., Jutand, A., Meyer, G., and Ntepe, A. N. Chem.-Eur. J. 2001, 7, 2134
216. Amatore, C., Jutand, A., and Thuilliez, A. J. Organomet. Chem. 2002, 643-644, 416
217. Barrios-Landeros, F. and Hartwig, J. F. J. Am. Chem. Soc. 2005, 127, 6944
218. Barrios-Landeros, F., Carrow, B. P., and Hartwig, J. F. J. Am. Chem. Soc. 2008, 130, 5842
219. Barrios-Landeros, F., Carrow, B. P., and Hartwig, J. F. J. Am. Chem. Soc. 2009, 131, 8141 and references therein
220. For selected mechanistic studies on reductive elimination for C-C bond formation
221. Culkin, D. A. and Hartwig, J. F. Organometallics 2004, 23, 3398
222. Racowski, J. M., Dick, A. R., and Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 10974
223. Stambuli, J. P., Incarvito, C. D., Bühl, M., and Hartwig, J. F. J. Am. Chem. Soc. 2004, 126, 1184
224. A 10-fold amount of carbonate and pivalate were used to mimic the relative base/palladium ratios that are found under the standard catalytic conditions. See Supporting Information for further experimental details.
225. Frisch, M. J. Gaussian 03, revision C.02; Gaussian, Inc.: Wallingford, CT, 2004.
226. Becke, A. D. J. Chem. Phys. 1993, 98, 5648
227. Lee, C., Yang, W., and Parr, R. G. Phys. Rev. B 1988, 37, 785
228. Schafer, A., Huber, C., and Ahlrichs, R. J. Chem. Phys. 1994, 100, 5829
229. Godbout, N., Salahub, D. R., Andzelm, J., and Wimmer, E. Can. J. Chem. 1992, 70, 560
230. Gorelsky, S. I. and Lever, A. B. P. J. Organomet. Chem. 2001, 635, 187
231. Gorelsky, S. I. AOMix: software for the MO Analysis, revision 6.35; University of Ottawa: Ottawa, 2007.
232. Barone, V., Cossi, M., and Tomasi, J. J. Comput. Chem. 1998, 19, 404
233. 3 and pivalate as acetate to minimize computational costs.
234. 3)-H bond cleavage is involved in the rate-determining step (Section 2.1).