Mechanisms of competitive ring-directed and side-chain-directed metalations in ortho-substituted toluenes

Organometallics

Volumn 15, Issue 15, 1996, Pages 3345-3359

  Kremer, Thomas ^a   Junge, Michael ^a   Schleyer, Paul Von Ragué ^a  

^a UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001243937     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960067o     Document Type: Article

References (96)

1. (a) Snieckus, V. Chem. Rev. 1990, 90, 879.
2. (b) Klumpp, G. W. Recl. Trav. Chim. Pays-Bas 1986, 105, 1.
3. (a) Gschwend, H. W.; Rodriguez, H. R. Org. React. 1979, 26, 1.
4. (b) Beak, P.; Snieckus, V. Acc. Chem. Res. 1982, 15, 306.
5. Wittig, G.; Fuhrmann, G. Chem. Ber. 1940, 73, 1197.
6. Gilman, H.; Bebb, R. L. J. Am. Chem. Soc. 1939, 61, 109.
7. Seebach, D.; Mässig, R.; Gabriel, J. Helv. Chim. Acta 1983, 66, 308.
8. Gilman, H.; Morton, J. W. Org. React. 1954, 8, 258.
9. Puterbaugh, W. H.; Hauser, C. R. J. Org. Chem. 1964, 29, 853.
10. Slocum, D. W.; Sugarmen, D. I. Adv. Chem. Ser. 1974, No. 130, 227.
11. Roberts, J. D.; Curtin, D. Y. J. Am. Chem. Soc. 1946, 68, 1658.
12. Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986, 19, 356.
13. (a) Wakefield, B. J. The Chemistry of Organolithium Compounds; Pergamon: Oxford, U.K., 1974.
14. (b) Beak, P.; Snieckus, V. Acc. Chem. Res. 1982, 15, 306.
15. (c) Wardell, J. L. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon: Oxford, U.K., 1982; Vol. 1, p 57.
16. (d) Narasimhan, N. S.; Mali, R. S. Synthesis 1983, 957.
17. (e) Beak, P.; Meyers, A. I. Acc. Chem. Res. 1986,19, 356.
18. (f) Narasimhan, N. S.; Mali, R. S. Top. Curr. Chem. 1987, 133, 63.
19. (g) Schlosser, M. In Modern Synthetic Methods; Scheffold, R., Ed.; VCH: Weinheim, Germany, 1992; p 227.
20. (h) Schlosser, M. In Organometallics in Synthesis; Schlosser, M., Ed.; Wiley-Interscience: New York, 1994.
21. Bauer, W.; Schleyer, P. v. R. J. Am. Chem. Soc. 1989, 111, 7191.
22. (a) van Eikema Hommes, N. J. R.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1992, 31, 755.
23. (b) van Eikema Hommes, N. J. R.; Schleyer, P. v. R. Tetrahedron 1994, 50, 5903.
24. Ludt, R. E.; Crowther, G. P.; Hauser, C. R. J. Org. Chem. 1970, 35, 1288.
25. Manzer, L. E. J. Am. Chem. Soc. 1978, 100, 8068.
26. (a) Brandsma, L.; Verkruijsse, H. Preparative Polar Organometallic Chemistry 1; Springer: Berlin, 1987.
27. (b) Brandsma, L. Preparative Polar Organometallic Chemistry 2; Springer: Berlin, 1990.
28. (c) Reference 16b, p 93.
29. Letsinger, R. L.; Schinzer, W. A. J. Org. Chem. 1951, 16, 869.
30. Harmon, T. E.; Shirley, D. A. J. Org. Chem. 1974, 39, 3164.
31. Gilman, H.; Soddy, T. S. J. Org. Chem. 1957, 22, 1715.
32. Takagishi, S.; Schlosser, M. Synlett 1991, 121.
33. (a) Suñer, G. A.; Deyá, P. M.; Saá, J. M. J. Am. Chem. Soc. 1990, 112, 1467.
34. (b) Saá, J. M.; Deyá, P. M.; Suñer, G. A.; Frontera, A. J. Am. Chem. Soc. 1992, 114, 9093.
35. (c) Katritzky, A. R.; Ignatchenko, A. V.; Lang, H.; Stevens, C. V.; Opitz, A.; Koch, R.; Anders, E. Tetrahedron 1994, 50, 6005.
36. (d) Cheney, V. B. J. Org. Chem. 1994, 59, 773.
37. (a) Anders, E.; Opitz, A.; van Eikema Hommes, N. J. R.; Hampel, F. J. Org. Chem. 1993, 58, 4424.
38. (b) Opitz, A.; Koch, R.; Katritzky, A. R.; Fan, W.-Q.; Anders, E. J. Org. Chem. 1995, 60, 3743.
39. (a) Stewart, J. J. P. J. Comput. Chem. 1989, 10, 209, 221.
40. (b) Anders, E.; Koch, R.; Freuntsch, P. J. Comput. Chem. 1993, 14, 1301.
41. (a) Dewar, M. J. S.; Thiel, W. J. Am. Chem. Soc. 1977, 99, 4899, 4907.
42. (b) Thiel, W.; Clark, T. QCPE 1982, No. 438.
43. Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory; Wiley: New York, 1986.
44. (a) Kaufmann, E.; Sehleyer, P. v. R.; Houk, K. N.; Wu, Y.-D. J. Am. Chem. Soc. 1985, 107, 5560.
45. (b) McKee, M. L. J. Am. Chem. Soc. 1987, 109, 559.
46. (c) Kaufmann, E.; Schleyer, P. v. R.; Gronert, S.; Streitwieser, A.; Halpern, M. J. Am. Chem. Soc. 1987, 109, 2553.
47. (d) Kaufmann, E.; Schleyer, P. v. R. J. Comput. Chem. 1989, 4, 437.
48. (e) Li, Y.; Paddon-Row, M. N.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 3684.
49. (f) Kaufmann, E.; Sieber, S.; Schleyer, P. v. R. J. Am. Chem. Soc. 1989, 111, 121.
50. (g) Kaufmann, E.; Sieber, S.; Schleyer, P. v. R. J. Am. Chem. Soc. 1989, 111, 4005.
51. (h) Leung-Toung, R.; Tidwell, T. T. J. Am. Chem. Soc. 1990, 112, 1042.
52. (i) Li, Y.; Paddon-Row, M. N.; Houk, K. N. J. Org. Chem. 1990, 55, 481.
53. (j) van Eikema Hommes, N. J. R.; Bühl, M.; Schleyer, P. v. R.; Wu, Y.-D. J. Organomet. Chem. 1991, 409, 307.
54. (k) van Eikema Hommes, N. J. R.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engt. 1992, 31, 755.
55. (l) Lambert, C.; Kaupp, M.; Schleyer, P. v. R. Organometallics 1993, 12, 853.
56. (m) Lambert, C.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1994, 33, 1129.
57. (n) Lambert, C.; Schleyer, P. v. R. in Methoden der organischen Chemie (Houben-Weyl); Georg Thieme Verlag Stuttgart, Germany, 1993; Vol E19d (Carbanions).
58. (o) Kremer, T.; Harder, S.; Junge, M.; Schleyer, P. v. R. Organometallics 1996, 15, 585.
59. (a) Ziegler, T. Chem. Rev. 1991, 91, 651.
60. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
61. (c) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
62. (a) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Wong, M. W.; Foresman, J. B.; Robb, M. A.; Head-Gordon, M.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P., Pople, J. A. Gaussian 92/DFT, Revision G.2; Gaussian, Inc., Pittsburgh, PA, 1993.
63. (b) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Peterson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanow, 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. J. P.; Head-Gordon, M.; Gonzalez, C., and Pople, J. A. GAUSSIAN 94; Gaussian, Inc., Pittsburgh, PA, 1995.
64. (a) NBO analysis: Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899 and references cited therein,
65. (b) NLMO bond orders: Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1990, 112, 1434.
66. (c) NPA charges: Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.
67. (a) Spitznagel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363.
68. (b) Clark, T.; Chandrasekhar, J.; Spitznagel, G. W.; Schleyer, P. v. R. J. Comput. Chem. 1983, 4, 294.
69. (c) Chandrasekhar, J.; Andrade, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1981, 103, 5609.
70. Szasz, L. Pseudopotential Theory of Atoms and Molecules; Wiley: New York, 1985.
71. (a) Müller, W.; Meyer, W. J .Chem. Phys. 1984, 80, 3311.
72. (b) Fuentealba, P.; Reyes, O.; Stoll, H.; Preuss, H. J. Chem. Phys. 1987, 87, 5338.
73. (c) Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1986, 85, 5158.
74. (d) Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1986, 84, 1687.
75. (e) Bauschlicher, C. W., Jr.; Langhoff, S. R.; Partridge, H. J. Chem. Phys. 1986, 84, 901.
76. (a) Partridge, H.; Bauschlicher, C. W., Jr.; Walch, S. P.; Liu, B. J. Chem. Phys. 1983, 79, 1866.
77. (b) Müller, W.; Flesch, J.; Meyer, W. J. Chem. Phys. 1984, 80, 3297.
78. (a) Kaupp, M.; Bergner, A.; Küchle, W.; Preuss, H.; Stoll, H., unpublished results,
79. (b) Huzinaga, S. Gaussian Basis Sets for Molecular Calculations; Elsevier: Amsterdam, 1984.
80. Fraser, R. R.; Bresse, M.; Mansour, T. S. J. Am. Chem. Soc. 1983, 105, 7790.
81. (a) Wenthold, P. G.; Squires, R. R. J. Am. Chem. Soc. 1994, 116, 6401.
82. (b) Lias, S. G.; Bartmess, J. E.; Liebmann, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. 1.
83. Katsoulos, G.; Takagishi, S.; Schlosser, M. Synlett 1991, 731.
84. (a) Kaufmann, E.; Tidor, B.; Schleyer, P. v. R. J. Comput. Chem. 1986, 7, 334.
85. (b) Kaufmann, E.; Gose, J.; Schleyer, P. v. R. Organometallics 1989, 8, 2577.
86. (a) Setzer, W. N.; Schleyer, P. v. R. Adv. Organomet. Chem. 1985, 24, 353.
87. (b) Schade, C.; Schleyer, P. v. R. Adv. Organomet. Chem. 1987, 27, 159.
88. (c) Weiss, E. Angew. Chem., Int. Ed. Engl. 1993, 32, 1501.
89. (d) Sapse, A. M.; Schleyer, P. v. R. Lithium Chemistry; Wiley-Interscience: New York, 1995.
90. Junge, M.; Kremer, T.; Sehleyer, P. v. R., paper in preparation.
91. Hoffmann, D.; Bauer, W.; Hampel, F.; van Eikema Hommes, N. J. R.; Otto, P.; Sehleyer, P. v. R.; Pieper, U.; Stahlke, D.; Snaith, R.; Wright, D. S. J. Am. Chem. Soc. 1994, 116, 528.
92. (a) Schleyer, P. v. R. Pure Appl. Chem. 1983, 55, 355.
93. (b) Schleyer, P. v. R. Pure Appl. Chem. 1984, 56, 151.
94. (a) Streitwieser, A. Ace. Chem. Res. 1984, 17, 353.
95. (b) Boche, G.; Etzrod, H.; Massa, W.; Baum, G. Angew. Chem., Int. Ed. Engl. 1985, 24, 863.
96. Allred, A. L.; Rochow, E. G. J. Inorg. Nucl. Chem. 1958, 5, 264.