Selective bromination of sp3 C-H bonds by organophotoredox catalysis

Asian Journal of Organic Chemistry

Volumn 3, Issue 4, 2014, Pages 536-544

  Kee, Choon Wee ^a,b   Chan, Ke Min ^b   Wong, Ming Wah ^b   Tan, Choon Hong ^a  

^a NANYANG TECHNOLOGICAL UNIVERSITY   (Singapore)

^b NATIONAL UNIVERSITY OF SINGAPORE   (Singapore)

Author keywords

Bromination; C H activation; Density functional calculations; Photoredox catalysis; Radical reactions

Indexed keywords

EID: 84898955703     PISSN: 21935807     EISSN: 21935807     Source Type: Journal    
DOI: 10.1002/ajoc.201300169     Document Type: Article

References (174)

1. K. Godula, D. Sames, Science 2006, 312, 67-72;
2. H. M. L. Davies, J. R. Manning, Nature 2008, 451, 417-424;
3. R. Giri, B.-F. Shi, K. M. Engle, N. Maugel, J.-Q. Yu, Chem. Soc. Rev. 2009, 38, 3242-3272;
4. I. A. I. Mkhalid, J. H. Barnard, T. B. Marder, J. M. Murphy, J. F. Hartwig, Chem. Rev. 2010, 110, 890-931;
5. "C-H activation": Top. Curr. Chem. Vol.292 (Eds.: J.-Q. Yu, Z.-J. Shi), Springer GmbH, 2010, p.384;
6. T. Newhouse, P. S. Baran, Angew. Chem. 2011, 123, 3422-3435; Angew. Chem. Int. Ed. 2011, 50, 3362-3374;
7. "C-H Functionalization in organic synthesis": Chem. Soc. Rev., Vol. 40 (Eds.: H.M.L. Davies, J. Du Bois, J.-Q. Yu), The Royal Society of Chemistry, 2011, pp.1845-2040;
8. "C-H functionalization": Acc. Chem. Res. Vol. 45 (Eds.: M.P. Doyle, K.I. Goldberg), American Chemical Society, 2012, pp.777-958;
9. L. McMurray, F. O'Hara, M. J. Gaunt, Chem. Soc. Rev. 2011, 40, 1885-1898;
10. H. Lu, X. P. Zhang, Chem. Soc. Rev. 2011, 40, 1899-1909;
11. C.-M. Che, V. K.-Y. Lo, C.-Y. Zhou, J.-S. Huang, Chem. Soc. Rev. 2011, 40, 1950-1975;
12. W. R. Gutekunst, P. S. Baran, Chem. Soc. Rev. 2011, 40, 1976-1991;
13. J. F. Hartwig, Chem. Soc. Rev. 2011, 40, 1992-2002;
14. C.-L. Sun, B.-J. Li, Z.-J. Shi, Chem. Rev. 2011, 111, 1293-1314;
15. K. M. Engle, T.-S. Mei, M. Wasa, J.-Q. Yu, Acc. Chem. Res. 2012, 45, 788-802;
16. T. Brückl, R. D. Baxter, Y. Ishihara, P. S. Baran, Acc. Chem. Res. 2012, 45, 826-839;
17. H. Chen, S. Schlecht, T. C. Semple, J. F. Hartwig, Science 2000, 287, 1995-1997;
18. J. Pan, M. Su, S. L. Buchwald, Angew. Chem. 2011, 123, 8806-8810; Angew. Chem. Int. Ed. 2011, 50, 8647-8651;
19. M. Wasa, K. S. L. Chan, X.-G. Zhang, J. He, M. Miura, J.-Q. Yu, J. Am. Chem. Soc. 2012, 134, 18570-18572;
20. A. A. Fokin, P. R. Schreiner, Adv. Synth. Catal. 2003, 345, 1035-1052.
21. M. Zhou, R. H. Crabtree, Chem. Soc. Rev. 2011, 40, 1875-1884; For selected works on the formation of C-O bond via C-H activation:
22. K. Chen, J. M. Richter, P. S. Baran, J. Am. Chem. Soc. 2008, 130, 7247-7249;
23. M. S. Chen, M. C. White, Science 2007, 318, 783-787;
24. M. S. Chen, M. C. White, Science 2010, 327, 566-571;
25. S. Das, C. D. Incarvito, R. H. Crabtree, G. W. Brudvig, Science 2006, 312, 1941-1943;
26. K. Kamata, K. Yonehara, Y. Nakagawa, K. Uehara, N. Mizuno, Nat. Chem. 2010, 2, 478-483;
27. C. Kim, K. Chen, J. Kim, L. Que, J. Am. Chem. Soc. 1997, 119, 5964-5965;
28. E. McNeill, J. D. Bois, J. Am. Chem. Soc. 2010, 132, 10202-10204;
29. E. M. Simmons, J. F. Hartwig, Nature 2012, 483, 70-73;
30. Y. Zhao, W.-L. Yim, C. K. Tan, Y.-Y. Yeung, Org. Lett. 2011, 13, 4308-4311.
31. T. Furuya, A. S. Kamlet, T. Ritter, Nature 2011, 473, 470-477;
32. D. A. Watson, M. Su, G. Teverovskiy, Y. Zhang, J. García-Fortanet, T. Kinzel, S. L. Buchwald, Science 2009, 325, 1661-1664;
33. K. S. L. Chan, M. Wasa, X. Wang, J.-Q. Yu, Angew. Chem. 2011, 123, 9247-9250; Angew. Chem. Int. Ed. 2011, 50, 9081-9084;
34. V. Rauniyar, A. D. Lackner, G. L. Hamilton, F. D. Toste, Science 2011, 334, 1681-1684;
35. X.-G. Zhang, H.-X. Dai, M. Wasa, J.-Q. Yu, J. Am. Chem. Soc. 2012, 134, 11948-11951;
36. M. Rueda-Becerril, C. ChatalovaSazepin, J. C. T. Leung, T. Okbinoglu, P. Kennepohl, J.-F. Paquin, G. M. Sammis, J. Am. Chem. Soc. 2012, 134, 4026-4029;
37. Z. Gao, Y. H. Lim, M. Tredwell, L. Li, S. Verhoog, M. Hopkinson, W. Kaluza, T. L. Collier, J. Passchier, M. Huiban, V. Gouverneur, Angew. Chem. 2012, 124, 6837-6841; Angew. Chem. Int. Ed. 2012, 51, 6733-6737.
38. S. Purser, P. R. Moore, S. Swallow, V. Gouverneur, Chem. Soc. Rev. 2008, 37, 320-330.
39. S. M. Ametamey, M. Honer, P. A. Schubiger, Chem. Rev. 2008, 108, 1501-1516.
40. P. Jeschke, ChemBioChem 2004, 5, 570-589.
41. M. H. Hung, W. B. Farnham, A. E. Feiring, S. Rozen in Fluoropolymers: synthesis, Vol.1 (Ed.: G. Hougham), Kluwer Academic/Plenum, New York, 1999, pp.51-66.
42. E. Erdik, Tetrahedron 1984, 40, 641-657;
43. Y. Sasson in Industrial Chemistry Library, Vol.7 (Eds.: B.G. Jean-RogerDesmurs, J.G. Melvin), Elsevier, 1995, pp.1-3;
44. D. P. Curran, Synthesis 1988, 3, 417-439;
45. A. Podgoršek, M. Zupan, J. Iskra, Angew. Chem. 2009, 121, 8576-8603; Angew. Chem. Int. Ed. 2009, 48, 8424-8450;
46. A. Rudolph, M. Lautens, Angew. Chem. 2009, 121, 2694-2708; Angew. Chem. Int. Ed. 2009, 48, 2656-2670; For a pioneering work on palladium-catalysed cross-coupling of alkyl halide:
47. T. Ishiyama, S. Abe, N. Miyaura, A. Suzuki, Chem. Lett. 1992, 21, 691-694.
48. W. Liu, J. T. Groves, J. Am. Chem. Soc. 2010, 132, 12847-12849;
49. W. Liu, X. Huang, M.-J. Cheng, R. J. Nielsen, W. A. Goddard, J. T. Groves, Science 2012, 337, 1322-1325.
50. R. Giri, X. Chen, J.-Q. Yu, Angew. Chem. 2005, 117, 2150-2153; Angew. Chem. Int. Ed. 2005, 44, 2112-2115.
51. P. R. Schreiner, O. Lauenstein, I. V. Kolomit syn, S. Nadi, A.A. Fokin, Angew. Chem. 1998, 110, 1993-1995; Angew. Chem. Int. Ed. 1998, 37, 1895-1897;
52. P. R. Schreiner, O. Lauenstein, E. D. Butova, P. A. Gunchenko, I. V. Kolomitsin, A. Wittkopp, G. Feder, A. A. Fokin, Chem. Eur. J. 2001, 7, 4996-5003.
53. S. Bloom, C. R. Pitts, D. C. Miller, N. Haselton, M. G. Holl, E. Urheim, T. Lectka, Angew. Chem. 2012, 124, 10732-10735; Angew. Chem. Int. Ed. 2012, 51, 10580-10583.
54. For selected works on the use of alkyl bromides in transition-metal-catalysed cross-coupling reactions:
55. D. W. Robbins, J. F. Hartwig, Angew. Chem. 2013, 125, 967-971; Angew. Chem. Int. Ed. 2013, 52, 933-937;
56. T. Hatakeyama, T. Hashimoto, Y. Kondo, Y. Fujiwara, H. Seike, H. Takaya, Y. Tamada, T. Ono, M. Nakamura, J. Am. Chem. Soc. 2010, 132, 10674-10676;
57. Z. Lu, G. C. Fu, Angew. Chem. 2010, 122, 6826-6828; Angew. Chem. Int. Ed. 2010, 49, 6676-6678;
58. C.-T. Yang, Z.-Q. Zhang, Y.-C. Liu, L. Liu, Angew. Chem. 2011, 123, 3990-3993; Angew. Chem. Int. Ed. 2011, 50, 3904-3907;
59. J. Zhou, G. C. Fu, J. Am. Chem. Soc. 2004, 126, 1340-1341.
60. H. Shaw, H. D. Perlmutter, C. Gu, S. D. Arco, T. O. Quibuyen, J. Org. Chem. 1997, 62, 236-237;
61. R. Montoro, T. Wirth, Synthesis 2005, 9, 1473-1478;
62. X. Jiang, M. Shen, Y. Tang, C. Li, Tetrahedron Lett. 2005, 46, 487-489.
63. C. Djerassi, Chem. Rev. 1948, 43, 271-317;
64. Z. Wang in Comprehensive Organic Name Reactions and Reagents, Wiley, 2010, p.3067.
65. T. Gan, R. Liu, P. Yu, S. Zhao, J. M. Cook, J. Org. Chem. 1997, 62, 9298-9304.
66. A. Albini, M. Alpegiani, Chem. Rev. 1984, 84, 43-71;
67. S. Protti, D. Dondi, M. Fagnoni, A. Albini, Green Chem. 2009, 11, 239-249;
68. A. Albini, V. Dichiarante, Photochem. Photobiol. Sci. 2009, 8, 248-254;
69. D. Ravelli, D. Dondi, M. Fagnoni, A. Albini, Appl. Catal. B 2010, 99, 442-447;
70. D. Ravelli, S. Protti, P. Neri, M. Fagnoni, A. Albini, Green Chem. 2011, 13, 1876-1884.
71. A. Albini, M. Fagnoni, M. Mella, Pure Appl. Chem. 2000, 72, 1321-1326;
72. M. Fagnoni, D. Dondi, D. Ravelli, A. Albini, Chem. Rev. 2007, 107, 2725-2756.
73. T. Bach, J. P. Hehn, Angew. Chem. 2011, 123, 1032-1077; Angew. Chem. Int. Ed. 2011, 50, 1000-1045.
74. K. Ohkubo, S. Fukuzumi, Org. Lett. 2000, 2, 3647-3650;
75. K. Ohkubo, K. Mizushima, R. Iwata, S. Fukuzumi, Chem. Sci. 2011, 2, 715-722;
76. Y. Yamada, T. Miyahigashi, H. Kotani, K. Ohkubo, S. Fukuzumi, J. Am. Chem. Soc. 2011, 133, 16136-16145;
77. K. Ohkubo, T. Kobayashi, S. Fukuzumi, Angew. Chem. 2011, 123, 8811-8814; Angew. Chem. Int. Ed. 2011, 50, 8652-8655;
78. S. Fukuzumi, K. Ohkubo, Chem. Sci. 2013, 4, 561-574.
79. J. Iriondo-Alberdi, M. F. Greaney, Eur. J. Org. Chem. 2007, 4801-4815.
80. C. L. Hill, Synlett 1995, 127-132;
81. B. S. Jaynes, C. L. Hill, J. Am. Chem. Soc. 1993, 115, 12212-12213;
82. B. S. Jaynes, C. L. Hill, J. Am. Chem. Soc. 1995, 117, 4704-4705.
83. N. Hoffmann, Chem. Rev. 2008, 108, 1052-1103;
84. N. Hoffmann, ChemSusChem 2012, 5, 352-371;
85. N. Hoffmann, Photochem. Photobiol. Sci. 2012, 11, 1613-1641.
86. S. Kamijo, T. Hoshikawa, M. Inoue, Org. Lett. 2011, 13, 5928-5931;
87. T. Hoshikawa, S. Kamijo, M. Inoue, Org. Biomol. Chem. 2013, 11, 164-169;
88. T. Hoshikawa, S. Yoshioka, S. Kamijo, M. Inoue, Synthesis 2013, 45, 874-887;
89. T. Hoshikawa, M. Inoue, Chem. Sci.- 2013. DOI:.
90. K. Tsutsumi, K. Terao, H. Yamaguchi, S. Yoshimura, T. Morimoto, K. Kakiuchi, T. Fukuyama, I. Ryu, Chem. Lett. 2010, 39, 828-829;
91. S. Kobayashi, T. Kawamoto, S. Uehara, T. Fukuyama, I. Ryu, Org. Lett. 2010, 12, 1548-1551;
92. I. Ryu, A. Tani, T. Fukuyama, D. Ravelli, M. Fagnoni, A. Albini, Angew. Chem. 2011, 123, 1909-1912; Angew. Chem. Int. Ed. 2011, 50, 1869-1872;
93. A. Fusano, S. Sumino, T. Fukuyama, I. Ryu, Org. Lett. 2011, 13, 2114-2117.
94. P. Esser, B. Pohlmann, H.-D. Scharfet, Angew. Chem. 1994, 106, 2093-2108; Angew. Chem. Int. Ed. Engl. 1994, 33, 2009-2023.
95. A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser, A. vonZelewsky, Coord. Chem. Rev. 1988, 84, 85-277.
96. T. P. Yoon, M. A. Ischay, J. Du, Nat. Chem. 2010, 2, 527-532.
97. J. M. R. Narayanam, C. R. J. Stephenson, Chem. Soc. Rev. 2011, 40, 102-113;
98. J. W. Tucker, C. R. J. Stephenson, J. Org. Chem. 2012, 77, 1617-1622.
99. D. Ravelli, M. Fagnoni, A. Albini, Chem. Soc. Rev. 2013, 42, 97-113.
100. D. Ravelli, M. Fagnoni, ChemCatChem 2012, 4, 169-171.
101. J. Xuan, W.-J. Xiao, Angew. Chem. 2012, 124, 6934-6944; Angew. Chem. Int. Ed. 2012, 51, 6828-6838.
102. L. Shi, W. Xia, Chem. Soc. Rev. 2012, 41, 7687-7697.
103. C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113, 5322-5363.
104. D. A. Nicewicz, D. W. C. MacMillan, Science 2008, 322, 77-80;
105. D. A. Nagib, M. E. Scott, D. W. C. MacMillan, J. Am. Chem. Soc. 2009, 131, 10875-10877;
106. P. V. Pham, D. A. Nagib, D. W. C. MacMillan, Angew. Chem. 2011, 123, 6243-6246; Angew. Chem. Int. Ed. 2011, 50, 6119-6122.
107. M. A. Ischay, M. E. Anzovino, J. Du, T. P. Yoon, J. Am. Chem. Soc. 2008, 130, 12886-12887;
108. J. Du, T. P. Yoon, J. Am. Chem. Soc. 2009, 131, 14604-14605;
109. M. A. Ischay, Z. Lu, T. P. Yoon, J. Am. Chem. Soc. 2010, 132, 8572-8574;
110. S. Lin, M. A. Ischay, C. G. Fry, T. P. Yoon, J. Am. Chem. Soc. 2011, 133, 19350-19353;
111. M. A. Ischay, M. S. Ament, T. P. Yoon, Chem. Sci. 2012, 3, 2807-2811.
112. A. G. Condie, J. C. González-Gómez, C. R. J. Stephenson, J. Am. Chem. Soc. 2010, 132, 1464-1465;
113. L. Furst, B. S. Matsuura, J. M. R. Narayanam, J. W. Tucker, C. R. J. Stephenson, Org. Lett. 2010, 12, 3104-3107;
114. C. Dai, J. M. R. Narayanam, C. R. J. Stephenson, Nat. Chem. 2011, 3, 140-145;
115. D. B. Freeman, L. Furst, A. G. Condie, C. R. J. Stephenson, Org. Lett. 2012, 14, 94-97;
116. J. D. Nguyen, J. W. Tucker, M. D. Konieczynska, C. R. J. Stephenson, J. Am. Chem. Soc. 2011, 133, 4160-4163;
117. L. Furst, J. M. R. Narayanam, C. R. J. Stephenson, Angew. Chem. 2011, 123, 9829-9833; Angew. Chem. Int. Ed. 2011, 50, 9655-9659;
118. C.-J. Wallentin, J. D. Nguyen, P. Finkbeiner, C. R. J. Stephenson, J. Am. Chem. Soc. 2012, 134, 8875-8884;
119. J. D. Nguyen, E. M. D'Amato, J. M. R. Narayanam, C. R. J. Stephenson, Nat. Chem. 2012, 4, 854-859.
120. M. Rueping, C. Vila, R. M. Koenigs, K. Poscharny, D. C. Fabry, Chem. Commun. 2011, 47, 2360-2362;
121. M. Rueping, S. Zhu, R. M. Koenigs, Chem. Commun. 2011, 47, 8679-8681;
122. M. Rueping, J. Zoller, D. C. Fabry, K. Poscharny, R. M. Koenigs, T. E. Weirich, J. Mayer, Chem. Eur. J. 2012, 18, 3478-3481;
123. S. Zhu, A. Das, L. Bui, H. Zhou, D. P. Curran, M. Rueping, J. Am. Chem. Soc. 2013, 135, 1823-1829;
124. T. Mitkina, C. Stanglmair, W. Setzer, M. Gruber, H. Kisch, B. Konig, Org. Biomol. Chem. 2012, 10, 3556-3561;
125. G. Zhao, C. Yang, L. Guo, H. Sun, C. Chen, W. Xia, Chem. Commun. 2012, 48, 2337-2339;
126. S. Maity, N. Zheng, Angew. Chem. 2012, 124, 9700-9704; Angew. Chem. Int. Ed. 2012, 51, 9562-9566;
127. M. Pirtsch, S. Paria, T. Matsuno, H. Isobe, O. Reiser, Chem. Eur. J. 2012, 18, 7336-7340;
128. F. R. Bou-Hamdan, P. H. Seeberger, Chem. Sci. 2012, 3, 1612-1616;
129. P. Wu, C. He, J. Wang, X. Peng, X. Li, Y. An, C. Duan, J. Am. Chem. Soc. 2012, 134, 14991-14999;
130. Y. Yasu, T. Koike, M. Akita, Angew. Chem. 2012, 124, 9705-9709; Angew. Chem. Int. Ed. 2012, 51, 9567-9571;
131. Y. Miyake, K. Nakajima, Y. Nishibayashi, J. Am. Chem. Soc. 2012, 134, 3338-3341;
132. S. Mizuta, S. Verhoog, K. M. Engle, T. Khotavivattana, M. O'Duill, K. Wheelhouse, G. Rassias, M. Médebielle, V. Gouverneur, J. Am. Chem. Soc. 2013, 135, 2505-2508.
133. M. Neumann, S. Füldner, B. König, K. Zeitler, Angew. Chem. 2011, 123, 981-985; Angew. Chem. Int. Ed. 2011, 50, 951-954;
134. H. Liu, W. Feng, C. W. Kee, Y. Zhao, D. Leow, Y. Pan, C.-H. Tan, Green Chem. 2010, 12, 953-956;
135. Y. Pan, C. W. Kee, L. Chen, C.-H. Tan, Green Chem. 2011, 13, 2682-2685;
136. Y. Pan, S. Wang, C. W. Kee, E. Dubuisson, Y. Yang, K. P. Loh, C.-H. Tan, Green Chem. 2011, 13, 3341-3344;
137. Y. C. Teo, Y. Pan, C. H. Tan, ChemCatChem 2013, 5, 235-240;
138. D. P. Hari, B. König, Org. Lett. 2011, 13, 3852-3855;
139. D. P. Hari, P. Schroll, B. König, J. Am. Chem. Soc. 2012, 134, 2958-2961;
140. K. Fidaly, C. Ceballos, A. Falguieres, M. S.-I. Veitia, A. Guy, C. Ferroud, Green Chem. 2012, 14, 1293-1297;
141. M. Neumann, K. Zeitler, Org. Lett. 2012, 14, 2658-2661.
142. M. E. Wolff, Chem. Rev. 1963, 63, 55-64.
143. F. Minisci, R. Galli, A. Galli, R. Bernardi, Tetrahedron Lett. 1967, 8, 2207-2209.
144. M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 2003, 24, 669-681;
145. Gaussian09, RevisionA.02, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Wallingford CT, 2009;
146. Y. Zhao, D. Truhlar, Theor. Chem. Acc. 2008, 120, 215-241;
147. C. E. Check, T. O. Faust, J. M. Bailey, B. J. Wright, T. M. Gilbert, L. S. Sunderlin, J. Phys. Chem. A 2001, 105, 8111-8116.
148. Y.-R. Luo in Handbook of Bond Dissociation Energies in Organic Compounds, CRC Press, Boca Raton, FL, 2002, pp.19-144.
149. J. M. Tedder, Angew. Chem. 1982, 94, 433-442; Angew. Chem. Int. Ed. Engl. 1982, 21, 401-410;
150. J. M. Tedder, Tetrahedron 1982, 38, 313-329;
151. B. P. Roberts, Chem. Soc. Rev. 1999, 28, 25-35.
152. G. A. Russell in Free radicals, Vol.1 (Ed.: J.K. Kochi), New York, 1973, p.275;
153. C. Walling, B. Miller, J. Am. Chem. Soc. 1957, 79, 4181-4187;
154. G. A. Russell, R. C. Williamson, J. Am. Chem. Soc. 1964, 86, 2357-2364;
155. R. E. Pearson, J. C. Martin, J. Am. Chem. Soc. 1963, 85, 3142-3146.
156. E.D. Glendening, J.K. Badenhoop, A.E. Reed, J.E. Carpenter, J.A. Bohmann, C.M. Morales, F. Weinhold, NBO 5.0., Theoretical Chemistry Institute, University of Wisconsin, Madison, 2001.
157. J. K. Badenhoop, F. Weinhold, J. Chem. Phys. 1997, 107, 5406-5421;
158. J. K. Badenhoop, F. Weinhold, Int. J. Quantum Chem. 1999, 72, 269-280.
159. R. L. Dorta, C. G. Francisco, E. Suarez, J. Chem. Soc. Chem. Commun. 1989, 0, 1168-1169.
160. G. Majetich, K. Wheless, Tetrahedron 1995, 51, 7095-7129.
161. P. Buchschacher, J. Kalvoda, D. Arigoni, O. Jeger, J. Am. Chem. Soc. 1958, 80, 2905-2906;
162. E. J. Corey, W. R. Hertler, J. Am. Chem. Soc. 1960, 82, 1657-1668;
163. D. H. R. Barton, J. M. Beaton, J. Am. Chem. Soc. 1961, 83, 4083-4089;
164. G. vanDeWoude, M. Biesemans, L. vanHove, Bull. Soc. Chim. Belg. 1980, 89, 993-1000.
165. C.Y. Legault, CYLview, 1.0.562 BETA, Université deSherbrooke, 2012.
166. P. G. M. Wuts, T. W. Greene in Greene's Protective Groups in Organic Synthesis, 4thed., Wiley-Interscience, Hoboken, NJ, Chichester, 2007, p.411.
167. G. A. Russell, J. Am. Chem. Soc. 1958, 80, 4997-5001.
168. A.-P. Schaffner, V. Darmency, P. Renaud, Angew. Chem. 2006, 118, 5979-5981; Angew. Chem. Int. Ed. 2006, 45, 5847-5849.
169. ≠ in this case is defined from the pre transition state complex to the relevant transition state structure. See pg. S116 and S137 in the Supporting Information for details.
170. Tunneling contribution was calculated by using an asymmetric Eckart potential with a Gaussian Post Processor:
171. B. C. Garrett, D. G. Truhlar, J. Phys. Chem. 1979, 83, 2921-2926;
172. A. Miyoshi, Gaussian Post Processor, rev. 2010.02.14m6, University of Tokyo, 2010. For an example of tunneling controlled reaction:
173. P. R. Schreiner, H. P. Reisenauer, D. Ley, D. Gerbig, C.-H. Wu, W. D. Allen, Science 2011, 332, 1300-1303.
174. 4 in the case of piperidine. See pg. S101 in the Supporting Information for a more in-depth discussion.