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For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
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For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
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0000754130
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For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
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0000844315
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For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
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For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
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For a discussion of the mechanism of the exchange involving aliphatic substrates, see: (a) Bailey, W. F.; Gagnier, R. P.; Patricia, J. J. J. Org. Chem. 1984, 49, 2098. (b) Newcomb, M.; Williams, W. G.; Crumpacker, E. L. Tetrahedron Lett. 1985, 26, 1183 (c) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T.; Wang, W. Tetrahedron Lett. 1986, 27, 1861. (d) Bailey, W. F.; Patricia, J. J.; Nurmi, T. T. Tetrahedron Lett. 1986, 27, 1865. (e) Ashby, E. C.; Pham, T. N. J. Org. Chem. 1987, 52, 1291. (f) Bailey, W. F.; Punzalan, E. R. J. Org. Chem. 1990, 55, 5404.
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0001763436
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For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
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0001645228
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For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
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0001763419
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For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
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0001066613
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For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
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85022693248
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For a discussion of the mechanism of Organolithium-aryl halide exchange, see: (a) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 964. (b) Winkler, H. J. S.; Winkler, H. J. Am. Chem. Soc. 1966, 88, 969. (c) Rogers, H. R.; Houk, J. J. Am. Chem. Soc. 1982, 104, 522. (d) Beak, P.; Allen, D. J.; Lee, W. K. J. Am. Chem. Soc. 1990, 112, 1629. (e) Beak, P.; Allen, D. J. J. Am. Chem. Soc. 1992, 114, 3420.
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Ward, H.R.1
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0039721948
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The 10-X-2 nomenclature follows a general classification of hypervalent N-X-L species, see: Perkins, C. W.; Martin, J. C.; Arduengo, A. J.; Lau, W.; Alegria, A.; Kochi, J. K. J. Am. Chem. Soc. 1980, 102, 7753.
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Kochi, J.K.6
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29
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0343657573
-
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Gilman's group appears to have been the first to suggest that lithium-halogen exchange may proceed via nucleophilic attack of an organolithium on the halogen atom of an organic halide. This early mechanistic formulation viewed the exchange as an SN2-like process in which a hypervalent 10-X-2 species would be the transition state, see: Sunthankar, S. V.; Gilman, H. J. Org. Chem. 1951, 16, 123.
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0002871621
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Wittig and Schöllkopf appear to have been the first to suggest that nucleophilic attack by an organolithium on the halogen atom of a substrate may give a 10-X-2 species as an intermediate, see: Wittig, G.; Schöllkopf, U. Tetrahedron Lett. 1958, 3, 91. The putative 10-X-2 intermediate was termed an "ate-complex" by Wittig, see: Wittig, G. Angew. Chem. 1958, 70, 65.
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Wittig, G.1
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0002871621
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Wittig and Schöllkopf appear to have been the first to suggest that nucleophilic attack by an organolithium on the halogen atom of a substrate may give a 10-X-2 species as an intermediate, see: Wittig, G.; Schöllkopf, U. Tetrahedron Lett. 1958, 3, 91. The putative 10-X-2 intermediate was termed an "ate-complex" by Wittig, see: Wittig, G. Angew. Chem. 1958, 70, 65.
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42
-
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0342787336
-
-
note
-
+. This species, which was prepared by Farnham and Calabrese (ref 15), was fully characterized but structural data were not reported.
-
-
-
-
43
-
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0010915020
-
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and references therein
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(a) Müller, M.; Stiasny, H. C.; Brönstrup, M.; Burton, A.; Hoffmann, R. W. J. Chem. Soc., Perkin Trans 2 1999, 731 and references therein.
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Hoffmann, R.W.5
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Hoffmann, R.W.6
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47
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0000073015
-
-
A recent theoretical investigation of the role of solvation on a model lithium-iodine exchange reaction between methyl iodide and vinyllithium indicates that introduction of a single water molecule as a ligand for lithium lowers the activation energy, leading to a 10-I-2 complex transition state for the process, see: Jedlicka, B.; Crabtree, R. H.; Siegbahn, P. E. M. Organometallics 1997, 16, 6021.
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Boche, G.1
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Frisch, M. J.; Trucks; G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb; M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortis, J. V.; Foresman, J. B.; Cioslowski, J.; Sefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 95, Development Version (Rev. D); Gaussian, Inc.: Pittsburgh, PA, 1995.
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Frisch, M.J.1
Trucks, G.W.2
Schlegel, H.B.3
Gill, P.M.W.4
Johnson, B.G.5
Robb, M.A.6
Cheeseman, J.R.7
Keith, T.8
Petersson, G.A.9
Montgomery, J.A.10
Raghavachari, K.11
Al-Laham, M.A.12
Zakrzewski, V.G.13
Ortis, J.V.14
Foresman, J.B.15
Cioslowski, J.16
Sefanov, B.B.17
Nanayakkara, A.18
Challacombe, M.19
Peng, C.Y.20
Ayala, P.Y.21
Chen, W.22
Wong, M.W.23
Andres, J.L.24
Replogle, E.S.25
Gomperts, R.26
Martin, R.L.27
Fox, D.J.28
Binkley, J.S.29
Defrees, D.J.30
Baker, J.31
Stewart, J.P.32
Head-Gordon, M.33
Gonzalez, C.34
Pople, J.A.35
more..
-
55
-
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0343221891
-
-
note
-
Detailed structural data may be found in the Supporting Information.
-
-
-
-
56
-
-
0343657567
-
-
note
-
2v symmetry are reported by Boche, Cioslowski, and co-workers (ref 19b) to be 22.6, 28.2, and 33.4 kcal/mol for X = I, Br, and Cl, respectively.
-
-
-
-
57
-
-
0343221889
-
-
note
-
3F. The calculated bond lengths for the lithium halides are 2.435 Å for LiI, 2.195 Å for LiBr, 2.055 Å for LiCl, and 1.584 Å for LiF.
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