Mechanism of anionic [3 + 2] cycloadditions. An ab initio computational study on the cycloaddition of allyl-, 2-borylallyl-, and 2-azaallyllithium to ethylene

Journal of the American Chemical Society

Volumn 120, Issue 14, 1998, Pages 3357-3370

  Neumann, Frank ^a   Lambert, Christoph ^b   Schleyer, Paul Von Ragué ^a  

^a UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^b UNIVERSITY OF REGENSBURG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; ANION; ETHYLENE; HETEROCYCLIC COMPOUND;

ANISOTROPY; ARTICLE; CALCULATION; POLARIZATION; REACTION ANALYSIS;

EID: 0032522104     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9735160     Document Type: Article

References (203)

1. (a) Kolobielski, M.; Pines, H. J. Am. Chem. Soc. 1957, 79, 5820.
2. (b) Shabtai, J.; Pines, H. J. Org. Chem. 1961, 26, 4225.
3. (a) For one intramolecular exception, see: Klumpp, G. W.; Schmitz, R. F. Tetrahedron Lett. 1974, 2911. For exceptions with Grignard reagents, see: (b) Duboudin, J.-G.; Jousseaume, B. Synth. Commun. 1979, 9, 53. (c) Duboudin, J.-G.; Jousseaume, B.; Pinet-Vallier, M. J. Organomet. Chem. 1979, 172, 1.
4. (a) For one intramolecular exception, see: Klumpp, G. W.; Schmitz, R. F. Tetrahedron Lett. 1974, 2911. For exceptions with Grignard reagents, see: (b) Duboudin, J.-G.; Jousseaume, B. Synth. Commun. 1979, 9, 53. (c) Duboudin, J.-G.; Jousseaume, B.; Pinet-Vallier, M. J. Organomet. Chem. 1979, 172, 1.
5. (a) For one intramolecular exception, see: Klumpp, G. W.; Schmitz, R. F. Tetrahedron Lett. 1974, 2911. For exceptions with Grignard reagents, see: (b) Duboudin, J.-G.; Jousseaume, B. Synth. Commun. 1979, 9, 53. (c) Duboudin, J.-G.; Jousseaume, B.; Pinet-Vallier, M. J. Organomet. Chem. 1979, 172, 1.
6. (a) Eidenschink, R.; Kauffmann, T. Angew. Chem. 1972, 84, 292; Angew. Chem., Int. Ed. Engl. 1972, 11, 292.
7. (a) Eidenschink, R.; Kauffmann, T. Angew. Chem. 1972, 84, 292; Angew. Chem., Int. Ed. Engl. 1972, 11, 292.
8. (b) Luteri, G. F.; Ford, W. T. J. Organomet. Chem. 1976, 105, 139.
9. (c) Luteri, G. F.; Ford, W. T. J. Org. Chem. 1977, 42, 820.
10. (a) Boche, G.; Martens, D. Angew. Chem. 1972, 84, 768; Angew. Chem., Int. Ed. Engl. 1972, 11, 724.
11. (a) Boche, G.; Martens, D. Angew. Chem. 1972, 84, 768; Angew. Chem., Int. Ed. Engl. 1972, 11, 724.
12. (b) Ford, W. T.; Luteri, G. F. J. Am. Chem. Soc. 1977, 99, 5330.
13. (c) Padwa, A.; Yeske, P. E. J. Am. Chem. Soc. 1988, 110, 1617.
14. (a) Bannwarth, W.; Eidenschink, R.; Kauffmann, T. Angew. Chem. 1974, 86, 476; Angew. Chem., Int. Ed. Engl. 1974, 13, 468
15. (a) Bannwarth, W.; Eidenschink, R.; Kauffmann, T. Angew. Chem. 1974, 86, 476; Angew. Chem., Int. Ed. Engl. 1974, 13, 468
16. (b) Kempf, D. J.; Wilson, K. D.; Beak, P. J. Org. Chem. 1982, 47, 1610.
17. (c) Beak, P.; Burg, D. A. Tetrahedron Lett. 1986, 27, 5911.
18. (d) Beak, P.; Wilson, K. D. J. Org. Chem. 1986, 51, 4627.
19. (e) Beak, P.; Wilson, K. D. J. Org. Chem. 1987, 52, 218.
20. (f) Beak, P.; Burg, D. A. J. Org. Chem. 1989, 54, 1647.
21. Marino, J. P.; Mesbergen, W. B. J. Am. Chem. Soc. 1974, 96, 4050.
22. (a) Yamago, S.; Nakamura, E. J. Am. Chem. Soc. 1989, 111, 7285.
23. (b) Nakamura, E.; Yamago, S.; Ejiri, S.; Dorigo, A. E.; Morokuma, K. J. Am. Chem. Soc. 1991, 113, 3183.
24. (c) Ejiri, S.; Yamago, S.; Nakamura, E. J. Am. Chem. Soc. 1992, 114, 8707.
25. (d) Prato M.; Suzuki, T.; Foroudian, H.; Li, Q.; Khemani, K.; Wudl, F.; Leonetti, J.; Little, R. D.; White, T.; Rickborn, B.; Yamago, S.; Nakamura, E. J. Am. Chem. Soc. 1993, 115, 1594.
26. (e) Yamago, S.; Ejiri, S.; Nakamura, E. Angew. Chem. 1995, 107, 2338; Angew. Chem., Int. Ed. Engl. 1995, 34, 2154.
27. (e) Yamago, S.; Ejiri, S.; Nakamura, E. Angew. Chem. 1995, 107, 2338; Angew. Chem., Int. Ed. Engl. 1995, 34, 2154.
28. (a) Kauffmann, T.; Berg, H.; Köppelmann, E. Angew. Chem. 1970, 82, 396; Angew. Chem., Int. Ed. Engl. 1970, 9, 380. For an early review, see:
29. (a) Kauffmann, T.; Berg, H.; Köppelmann, E. Angew. Chem. 1970, 82, 396; Angew. Chem., Int. Ed. Engl. 1970, 9, 380. For an early review, see:
30. (b) Kauffmann, T. Angew. Chem. 1974, 86, 715; Angew. Chem., Int. Ed. Engl. 1974, 13, 627.
31. (b) Kauffmann, T. Angew. Chem. 1974, 86, 715; Angew. Chem., Int. Ed. Engl. 1974, 13, 627.
32. (a) Kauffmann, T.; Köppelmann, E. Angew. Chem. 1972, 84, 261; Angew. Chem., Int. Ed. Engl. 1972, 11, 290.
33. (a) Kauffmann, T.; Köppelmann, E. Angew. Chem. 1972, 84, 261; Angew. Chem., Int. Ed. Engl. 1972, 11, 290.
34. (b) Kauffmann T.; Habersaat, K.; Köppelmann, E. Angew. Chem. 1972, 84, 262; Angew. Chem. Int. Ed. Engl. 1972, 11, 291.
35. (b) Kauffmann T.; Habersaat, K.; Köppelmann, E. Angew. Chem. 1972, 84, 262; Angew. Chem. Int. Ed. Engl. 1972, 11, 291.
36. Kauffmann, T.; Busch, A.; Habersaat, K.; Scheerer, B. Tetrahedron Lett. 1973, 4047.
37. Sinbandhit, S.; Hamelin, J. J. Chem. Soc., Chem. Commun. 1977, 768.
38. (e) Kauffmann, T.; Habersaat K.; Köppelmann, E. Chem. Ber. 1977, 110, 638.
39. (f) Dryanska V.; Popandova-Yambolieva, K.; Ivanov, C. Tetrahedron Lett. 1979, 443.
40. (g) Grigg, R.; Kemp, J.; Malone, J.; Tangthongkum, A. J. Chem. Soc., Chem. Commun. 1980, 648.
41. (h) Dehnel, H.; Lavielle, G. Tetrahedron Lett. 1980, 21, 1315.
42. Cawkill, E.; Clark, N. G. J. Chem. Soc., Perkin Trans. 1 1980, 244.
43. (j) Fouchet, B.; Joucla, M.; Hamelin, J. Tetrahedron Lett. 1981, 22, 3397.
44. (k) Rabiller, C.; Dehnel, A.; Lavielle, G. Can. J. Chem. 1982, 60, 926.
45. Dryanska, V.; Popandova, K.; Ivanov, C. Synth. Common. 1982, 12, 343.
46. Parker, K. A.; Cohen, I. D.; Babine, R. E. Tetrahedron Lett. 1984, 25, 3543.
47. (n) Tsuge, O.; Kanemasa, S.; Hatada, A.; Matsuda, K. Bull. Chem. Soc. Jpn. 1986, 59, 2537.
48. (o) Grigg, R.; Devlin, J. J. Chem. Soc., Chem. Commun. 1986, 631.
49. (p) Pearson, W. H.; Walters, M. A.; Oswell, K. D. J. Am. Chem. Soc. 1986, 108, 2769.
50. (q) Grigg, R.; Sridharan, V.; Thianpatanagul, S. J. Chem. Soc., Perkin Trans. 1 1986, 1669.
51. (r) Tsuge, O.; Kanemasa, S.; Yamada, T.; Matsuda, K. J. Org. Chem. 1987, 52, 2523.
52. (s) Tsuge, O.; Kanemasa, S.; Yoshioka, M. J. Org. Chem. 1988, 3, 1384.
53. (t) Pearson, W. H.; Szura, D. P.; Harter, W. G. Tetrahedron Lett. 1988, 29, 761.
54. (u) Barr, D. A.; Grigg, R.; Gunaratne, N.; Kemp, J.; McMeekin P.; Sridharan, V. Tetrahedron 1988, 44, 557.
55. Dehnel, A.; KanabusKaminska, J. M.; Lavielle, G. Can. J. Chem. 1988, 66, 310.
56. (w) Kanemasa S.; Yoshioka, M.; Tsuge, O. Bull. Chem. Soc. Jpn. 1989, 62, 2196
57. Amornraska, K.; Barr, D.; Donegan, G.; Grigg R.; Ratananukul, P.; Sridharan, V. Tetrahedron 1989, 45, 4649.
58. (y) Barr, D. A.; Grigg, R.; Sridharan, V. Tetrahedron Lett. 1989, 30, 4727.
59. (z) Kanemasa, S.; Yoshioka, M.; Tsuge, O. Bull. Chem. Soc. Jpn. 1989, 62, 869.
60. (aa) Kanemasa, S.; Uchida, O.; Wada, E.; Yamamoto, H. Chem. Lett. 1990, 105.
61. (bb) Pearson, W. H.; Szura, D. P.; Postich, M. J. J. Am. Chem. Soc. 1992, 114, 1329.
62. Pearson, W. H.; Postich, M. J. J. Org. Chem. 1992, 57, 6354.
63. (a) Popowski, E. Z. Chem. 1974, 14, 360.
64. (b) Kauffmann, T.; Ahlers, H.; Hamsen, A.; Schulz, H.; Tilhard, H-J.; Vahrenhorst, A. Angew. Chem. 1977, 89, 107; Angew. Chem., Int. Ed. Engl. 1977, 16, 119.
65. (b) Kauffmann, T.; Ahlers, H.; Hamsen, A.; Schulz, H.; Tilhard, H-J.; Vahrenhorst, A. Angew. Chem. 1977, 89, 107; Angew. Chem., Int. Ed. Engl. 1977, 16, 119.
66. Kauffmann, T. Top. Curr. Chem. 1980, 92, 109.
67. Kauffmann, T.; Ahlers, H.; Echsler, K.-J.; Schulz, H.; Tilhard, H.-J. Chem. Ber. 1985, 118, 4496.
68. (a) Kauffmann, T.; Eidenschink, R. Angew. Chem. 1971, 83, 794; Angew. Chem., Int. Ed. Engl. 1971. 10, 739.
69. (a) Kauffmann, T.; Eidenschink, R. Angew. Chem. 1971, 83, 794; Angew. Chem., Int. Ed. Engl. 1971. 10, 739.
70. (b) Kauffmann, T.; Eidenschink, R. Chem. Ber. 1977, 110, 645.
71. Vo Quang, L.; Vo Quang, Y. Tetrahedron Lett. 1978, 4679.
72. Vo Quang, L.; Gaessler, H.; Vo Quang, Y. Angew. Chem. 1981, 93, 922; Angew. Chem., Int. Ed. Engl. 1981, 20, 880.
73. Vo Quang, L.; Gaessler, H.; Vo Quang, Y. Angew. Chem. 1981, 93, 922; Angew. Chem., Int. Ed. Engl. 1981, 20, 880.
74. (a) Kauffmann, T.; Busch, A.; Habersaat, K.; Köppelmann, E. Angew. Chem. 1973, 85, 584; Angew. Chem., Int. Ed. Engl. 1973, 12, 569.
75. (a) Kauffmann, T.; Busch, A.; Habersaat, K.; Köppelmann, E. Angew. Chem. 1973, 85, 584; Angew. Chem., Int. Ed. Engl. 1973, 12, 569.
76. (b) Kauffmann, T.; Busch, A.; Habersaat, K.; Köppelmann, E. Chem. Ber. 1983, 116, 492.
77. (a) Kauffmann, T.; Berg, H.; Ludorff, E.; Woltermann, A. Angew. Chem. 1970, 82, 986; Angew. Chem., Int. Ed. Engl. 1970, 9, 960.
78. (a) Kauffmann, T.; Berg, H.; Ludorff, E.; Woltermann, A. Angew. Chem. 1970, 82, 986; Angew. Chem., Int. Ed. Engl. 1970, 9, 960.
79. (b) Kauffmann, T.; Eidenschink, R. Angew. Chem. 1973, 85, 583; Angew. Chem. Int. Ed. Engl. 1973, 12, 568.
80. (b) Kauffmann, T.; Eidenschink, R. Angew. Chem. 1973, 85, 583; Angew. Chem. Int. Ed. Engl. 1973, 12, 568.
81. Kauffmann, T.; Eidenschink, R. Chem.'Ber. 1977, 110, 651.
82. (a) Nibbering, N. M. M. in Kinetics of Ion - Molecule Reactions; NATO ASI Series B40; Ausloos, P., Ed.; Plenum Press: New York, 1979; p 165.
83. (b) Dawson, J. H. J.; Nibbering, N. M. M. Int. J. Mass Spectrom. Ion. Phys. 1980, 33, 3.
84. Nibbering, N. M. M. Recl. Trav. Chim. Pays-Bas 1981, 100, 297.
85. Kleingeld, J. C.; Nibbering, N. M. M. Recl. Trav. Chim. Pays-Bas 1984, 103, 87.
86. (a) Woodward, R. B.; Hoffmann, R. Angew. Chem. 1969, 81, 797; Angew;. Chem., Int. Ed. Engl. 1969, 8, 781.
87. (a) Woodward, R. B.; Hoffmann, R. Angew. Chem. 1969, 81, 797; Angew;. Chem., Int. Ed. Engl. 1969, 8, 781.
88. (b) Woodward, R. B.; Hoffmann, R. The Conservation of Orbital Symmetry; Academic Press: New York, 1970.
89. For secondary kinetic isotope effect measurements, see: (a) Seltzer, S. J. Am. Chem. Soc. 1963, 85, 1360.
90. (b) van Sickle, D. E.; Rodin, J. O. J. Am. Chem. Soc. 1964, 86, 6, 3091.
91. Seltzer, S. J. Am., Chem. Soc. 1965, 87, 1534.
92. Goldstein, M. J.; Thayer, G. L., Jr. J. Am. Chem. Soc. 1965, 87, 1933.
93. (e) Taagepera, M.; Thornton, E. R. J. Am. Chem. Soc. 1972, 94, 1168.
94. (f) Gajewski, J. J.; Conrad, N. D. J. Am. Chem. Soc. 1979, 101, 6693.
95. (g) Gajewski, J. J.; Peterson, K. B.; Kagel, J. R. J. Am. Chem. Soc. 1987, 109, 5545.
96. (h) Baldwin, J. E.; Reddy, V. P.; Hess, B. A., Jr.; Schaad, L. J. J. Am. Chem. Soc. 1988, 110, 8554.
97. Baldwin, J. E.; Reddy, V. P.; Hess, B. A., Jr.; Schaad, L. J. J. Am. Chem. Soc. 1988, 110, 8555.
98. (j) Gajewsta, J. J.; Peterson, K. B.; Kagel, J. R.; Huang, Y. C. J. J. Am. Chem. Soc. 1989, 111, 9078.
99. (k) Singleton, D. A.; Thomas, A. A. J. Am. Chem. Soc. 1995, 117, 9357.
100. Beno, B. R.; Houk, K. N.; Singleton, D. A. J. Am. Chem. Soc. 1996, 118, 9984. For ab initio calculations of secondary kinetic isotope effects, see:
101. Houk, K. N.; Gustafson, S. M.; Black, K. A. J. Am. Chem. Soc. 1992, 114, 8565.
102. (n) Storer, J. W.; Raimondi, L.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 9675.
103. (o) Wiest, O.; Black, K. A.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 10336.
104. (p) Yoo, H. Y.; Houk, K. N. J. Am. Chem. Soc. 1994, 116, 12047.
105. (q) Houk, K. N.; Li, Y.; Storer, J.; Raimondi, L.; Beno, B. J. Chem. Soc., Faraday Trans. 1994, 90, 1599.
106. (r) Wiest, O.; Houk, K. N.; Black, K. A.; Thomas, B. J. Am. Chem. Soc. 1995, 117, 8594.
107. (s) Goldstein, E.; Beno, B.; Houk, K. N. J. Am. Chem. Soc. 1996, 118, 6036.
108. Sauers, R. R. Tetrahedron Lett. 1996, 37, 7679.
109. (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 F.2; Gaussian, Inc.: Pittsburgh, PA, 1993.
110. (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.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. M.; 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 94, Revision B.2; Gaussian, Inc.: Pittsburgh, PA, 1995.
111. Frisch, M. J.; Foresman, J. B.; Frisch, Æ. Gaussian 92 User's Guide; Gaussian, Inc.: Pittsburgh, PA, 1992.
112. Gaussian 92/DFT, New Methods and Features in Gaussian 92/DFT; Gaussian, Inc.: Pittsburgh, PA, 1993.
113. (a) Spitznagel, G. W.; Clark, T.; Chandrasekhar, J.; Schleyer, P. v. R. J. Comput. Chem. 1982, 3, 363.
114. (b) Chandrasekhar, J.; Andrade, J. G.; Schleyer, P. v. R. J. Am. Chem. Soc. 1981, 103, 5609.
115. (a) Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab initio Molecular Orbital Theory; John Wiley & Sons: New York, 1986.
116. (b) Foresman, J. B.; Frisch, Æ. Exploring Chemistry with Electronic Structures Methods: A Guide to Using Gaussian; Gaussian, Inc.: Pittsburgh, PA, 1993.
117. (a) Stevens, P. J.; Devlin, F. J.; Chebolowski, C. F.; Frisch, M. J. J. Phys. Chem. 1994, 98, 11623.
118. (b) Labanowski, J. W.; Andzelm, J. Density Functional Methods in Chemistry, Springer: New York, 1991.
119. Parr, R. G.; Yang, W. Density Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
120. Becke, A. D. J. Chem. Phys. 1993, 98, 5648. For a recent review on the suitability of density functional calculations for the study of pericyclic reactions, see:
121. (e) Wiest, O.; Houk, K. N. Top. Curr. Chem. 1996, 183, 2.
122. (f) Houk, K. N.; Beno, B. R.; Nendel, M.; Black, K.; Yoo, H. Y.; Wilsey, S.; Lee, J. K. J. Mol. Struct. (THEOCHEM) 1997, 398-399, 169.
123. Raghavachari, K.; Binkley, J. S.; Seeger, R.; Pople, J. A. J. Chem. Phys. 1980, 72, 650.
124. Unsubstituted and alkyl-substituted allylic compounds, NMR, kinetic, and UV spectroscopic studies: (a) West, P.; Purmort, J. I.; McKinley, S. V. J. Am. Chem. Soc. 1968, 90, 797.
125. (b) West, P.; Waack, R.; Purmort, J. I. J. Am. Chem. Soc. 1970, 92, 2, 840.
126. Scherr, P. A.; Hogan, R. J.; Oliver, J. P. J. Am. Chem. Soc. 1974, 96, 6055.
127. Dongen, J. P. C. M. v.; Dijkman, H. W. D. v.; Bie, M. J. A. d. Recl. Trav. Chim. Pays-Bas 1974, 93, 29.
128. (e) Thompson, T. B.; Ford, W. T. J. Am. Chem. Soc. 1979, 101, 5459.
129. (f) Neugebauer, W.; Schleyer, P. v. R. J. Organomet. Chem. 1980, 198, C1.
130. (g) Schlosser, M.; Stähle, M. Angew. Chem. 1980, 92, 497; Angew. Chem., Int. Ed. Engl. 1980, 19, 487.
131. (g) Schlosser, M.; Stähle, M. Angew. Chem. 1980, 92, 497; Angew. Chem., Int. Ed. Engl. 1980, 19, 487.
132. (h) Brownstein, S.; Bywater, S.; Worsfold, D. J. J. Organomet. Chem. 1980, 199, 1.
133. Winchester, W. R.; Bauer, W.; Schleyer, P. v. R. J. Chem. Soc., Chem. Commun. 1987, 177. For X-ray structures, see:
134. (j) Schürmann, U.; Weiss, E.; Dietrich, H.; Mahdi, W. J. Organomet. Chem. 1987, 322, 299.
135. (k) Köster, H.; Weiss, E. Chem. Ber. 1982, 115, 3422.
136. Marsch, M.; Harms, K.; Massa, W.; Boche, G. Angew. Chem. 1987, 99, 706; Angew. Chem., Int. Ed. Engl. 1987, 26, 6, 696.
137. Marsch, M.; Harms, K.; Massa, W.; Boche, G. Angew. Chem. 1987, 99, 706; Angew. Chem., Int. Ed. Engl. 1987, 26, 6, 696.
138. Seebach, D.; Maetzke, T.; Haynes, R. K.; Paddon-Row: M. N.; Wong, S. S. Helv. Chim. Acta 1988, 71, 299.
139. (n) Boche, G.; Fraenkel, G.; Cabral, J.; Harms, K.; Hommes, N. J. R. v. E.; Lohrenz, J.; Marsch, M.; Schleyer, P. v. R. J. Am. Chem. Soc. 1992, 114, 1562.
140. Aryl-substituted allylic compounds, NMR and UV/vis studies: (a) Heiszwolf, G. J.; Kloosterziel, H. Recl. Trav. Chim. Pays-Bas 1967, 86, 1345.
141. (b) Freedman, H. H.; Sandel, V. R.; Thill, B. P. J. Am. Chem. Soc. 1967, 89, 1762.
142. Sandel, V. R.; McKinley, S. V.; Freedman, H. H. J. Am. Chem. Soc. 1968, 90, 495.
143. Burley, J. W.; Young, R. N. J. Chem. Soc., Chem. Commun. 1969, 1127.
144. (e) Burley, J. W.; Ife, R.; Young, R. N. J. Chem. Soc., Chem. Commun. 1970, 1256.
145. (f) Burley, J. W.; Young, R. N. J. Chem. Soc. B 1971, 1018.
146. (g) Burley, J. W.; Young, R. N. J. Chem. Soc., Perkin Trans. 2 1972, 835.
147. (h) Burley, J. W.; Young, R. N. J. Chem. Soc., Perkin Trans. 2 1972, 1006.
148. Burley, J. W.; Young, R. N. J. Chem. Soc., Perkin Trans. 2 1972, 1843.
149. (j) Bushby, R. J.; Ferber, G. J. Tetrahedron Lett. 1974, 3701.
150. (k) Greenacre, G. C.; Young, R. N. J. Chem. Soc., Perkin Trans. 2 1975, 1661.
151. Boche, G.; Schneider, D. R. Tetrahedron Lett. 1976, 3657.
152. Bushby, R. J.; Ferber, G. J. J. Chem. Soc., Perkin Trans. 2 1976, 1688.
153. (n) Boche, G.; Martens, D.; Wagner, H.-U. J. Am. Chem. Soc. 1976, 98, 2668.
154. (o) Parkes, H. M.; Young, R. N. J. Chem. Soc., Perkin Trans. 2 1978, 249.
155. (p) Bushby, R. J. J. Chem. Soc., Perkin Trans. 2 1980, 1419. For X-ray structures, see:
156. (q) Boche, G.; Etzrodt, H.; Marsch, M.; Massa, W.; Baum, G.; Dietrich, H.; Mahdi, W. Angew. Chem. 1986, 98, 84; Angew. Chem., Int. Ed. Engl. 1986, 25, 104.
157. (q) Boche, G.; Etzrodt, H.; Marsch, M.; Massa, W.; Baum, G.; Dietrich, H.; Mahdi, W. Angew. Chem. 1986, 98, 84; Angew. Chem., Int. Ed. Engl. 1986, 25, 104.
158. (r) Bock, H.; Ruppert, K.; Havlas, Z.; Fenske, D. Angew. Chem. 1990, 102, 1095; Angew. Chem., Int. Ed. Engl. 1990, 29, 1042.
159. (r) Bock, H.; Ruppert, K.; Havlas, Z.; Fenske, D. Angew. Chem. 1990, 102, 1095; Angew. Chem., Int. Ed. Engl. 1990, 29, 1042.
160. (s) Ahlbrecht, H.; Boche, G.; Harms, K.; Marsch, M.; Sommer, H. Chem. Ber. 1990, 123, 1853.
161. (t) Corbelin, S.; Kopf, J.; Lorenzen, N. P.; Weiss, E. Angew. Chem. 1991, 103, 875; Angew. Chem., Int. Ed. Engl. 1991, 30, 825.
162. (t) Corbelin, S.; Kopf, J.; Lorenzen, N. P.; Weiss, E. Angew. Chem. 1991, 103, 875; Angew. Chem., Int. Ed. Engl. 1991, 30, 825.
163. (a) Bongini, A.; Cainelli, G.; Cardillo, G.; Palmieri, P.; Umani-Ronchi, A. J. Organomet. Chem. 1976, 110, 1.
164. (b) Clark, T.; Jemmis, E. D.; Schleyer, P. v. R.; Binkley, J. S.; Pople, J. A. J. Organomet. Chem. 1978, 150, 1.
165. Clark, T.; Rohde, C.; Schleyer, P. v. R. Organometallics 1983, 2, 1344.
166. Schleyer, P. v. R. J. Am. Chem. Soc. 1985, 107, 4793.
167. (e) Wiberg, K. B.; Breneman, C. M.; LePage, T. J. J. Am. Chem. Soc. 1990, 112, 61.
168. (f) Hommes, N. J. R. v. E.; Bühl, M.; Schleyer, P. v. R.; Wu, Y.-D. J. Organomet. Chem. 1991, 409, 307.
169. (g) Gobbi, A.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 9275.
170. (h) Lambert, C.; Schleyer, P. v. R. Angew. Chem. 1994, 106, 1187; Angew. Chem., Int. Ed. Engl. 1994, 33, 1129.
171. (h) Lambert, C.; Schleyer, P. v. R. Angew. Chem. 1994, 106, 1187; Angew. Chem., Int. Ed. Engl. 1994, 33, 1129.
172. For an UV/vis spectroscopic study of ion pairing and cis/trans isomerization of 1,3-diphenyl-2-azaallyllithium, see: (a) Young, R. N.; Ahmad, M. A. J. Chem. Soc., Perkin Trans. 2 1982, 35. For an X-ray structure of its sodium derivative as complex with PMDETA, see:
173. (b) Andrews, P. C.; Mulvey, R. E.; Clegg, W.; Reed, D. J. Organomet. Chem. 1990, 386, 287. For a theoretical study of 2-azaallyl anion, see ref 23d. For computations on 2-azaallylsodium, see:
174. Andrews, P. C.; Armstrong, D. R.; Mulvey, R. E.; Reed, D. J. Am. Chem. Soc. 1988, 110, 5235.
175. An ab initio computational study on cyclopropylboryl and 2-methyleneboratirane systems, which are isomers of the 2-borylallyl compounds considered here, will be published shortly.
176. For a review on boron-stabilized carbanions, see: (a) Pelter, A.; Smith, K. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Schreiber, S. L., Eds.; Pergamon Press: Oxford, 1991; Vol. 1, p 487. For X-ray structures of such species, see:
177. (b) Bartlett, R. A.; Power, P. P. Organometallics 1986, 5, 1916.
178. Olmstead, M. M.; Power, P. P.; Weese, K. J., Doedens, R. J. J. Am. Chem. Soc. 1987, 109, 2541.
179. At Becke3LYP/6-311++G**//MP2(fc)6-31+G* + 0.89 ZPE (HF/ 6-31+G*).
180. (a) El-Nahas, A.; Schleyer, P. v. R. J. Comput. Chem. 1994, 15, 596.
181. (b) Schleyer, P. v. R.; Chandrasekhar, J.; Kos, A. J.; Clark, T.; Spitznagel, G. W. J. Chem. Soc., Chem. Commun. 1981, 882.
182. Boese, R.; Bläser, D.; Niederprüm, N.; Nüsse, M.; Brett, W. A.; Schleyer, P. v. R.; Bühl, M.; Hommes, N. J. R. v. E. Angew. Chem. 1992, 104, 356; Angew. Chem., Int. Ed. Engl. 1992, 31, 314.
183. Boese, R.; Bläser, D.; Niederprüm, N.; Nüsse, M.; Brett, W. A.; Schleyer, P. v. R.; Bühl, M.; Hommes, N. J. R. v. E. Angew. Chem. 1992, 104, 356; Angew. Chem., Int. Ed. Engl. 1992, 31, 314.
184. s form (c, d): (a) Cremer, D.; Pople, J. A. J. Am. Chem. Soc. 1975, 97, 1358.
185. (b) Saebø, S.; Cordell, F.; Boggs, J. E. J. Mol. Struct. (THEOCHEM) 1983, 104, 221.
186. Hoyland, J. R. J. Chem. Phys. 1969, 50, 2775.
187. Ferguson, D. M.; Could, I. R.; Glauser, W. A.; Schroeder, S.; Kollman, P. A. J. Comput. Chem. 1992, 13, 525. Experimental studies (thermodynamic, infrared spectroscopy, and electron diffraction) revealed that the cyclopentane ring is puckered. The puckering displacement was shown to move freely around the ring (pseudorotation). See:
188. (e) Adams, W. J.; Geise, H. J.; Bartell, L. S. J. Am. Chem. Soc. 1970, 92, 5013 and references therein.
189. (f) Fuchs, B. In Topics in Stereochemistry; Eliel, E. L., Allinger, N. L., Eds.; Wiley & Sons: New York, 1978; p 1.
190. (g) Legon, A. C. Chem. Rev. 1980, 80, 231.
191. However, similar to cyclopentane, the barrier for pseudorotation of the pyrrolidine ring has been found to be very small: (a) Pfafferott, G.; Oberhammer, H.; Boggs, J. E.; Caminati, W. J. Am. Chem. Soc. 1985, 107, 2305.
192. (b) Armstrong, D. R.; Barr, D.; Clegg, W.; Mulvey, R. E.; Reed, D.; Snaith, R.; Wade, K. J. Chem. Soc., Chem. Commun. 1986, 869.
193. Armstrong, D. R.; Barr, D.; Clegg, W.; Hodgson, S. M.; Mulvey, R. E.; Reed, D.; Snaith, R.; Wright, D. S. J. Am. Chem. Soc. 1989, 111, 4719.
194. acid are as follow. Propene, 390.8 kcal/mol: Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas-Phase Ion and Neutral Thermochemistry; American Institute of Physics: Williston, VT, 1988. Cyclopropane, 416.1 kcal/mol: DePuy, C. H.; Gronert, S.; Barlow, S. E.; Bierbaum, V. M.; Damrauer, R. J. Am. Chem. Soc. 1989, 111, 1968.
195. acid are as follow. Propene, 390.8 kcal/mol: Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. Gas-Phase Ion and Neutral Thermochemistry; American Institute of Physics: Williston, VT, 1988. Cyclopropane, 416.1 kcal/mol: DePuy, C. H.; Gronert, S.; Barlow, S. E.; Bierbaum, V. M.; Damrauer, R. J. Am. Chem. Soc. 1989, 111, 1968.
196. The geometry reported for 33 by Sauers (ref 17) at MP2/6-31+G* differs slightly from ours: the critical C-C distance of 2.279 Å is 0.093 Å shorter, and three imaginary frequencies were calculated for this structure at MP2/6-31+G*.
197. Relative energies of products at Becke3LYP/6-311+G**/ /Becke3LYP/6-311+G**: 8, -0.6; 9, -0.5; 10, 0.7; 11, -0.6; 12, -45.3; 15, -36.4; 18, -31.1; 20, -16.3; 21, -25.6.
198. For the influence of basis sets and electron correlation on the calculation of molecular polarizabilities, see: (a) Gough, K. M. J. Chem. Phys. 1989, 91, 2424.
199. (b) Spackman, M. A. J. Phys. Chem. 1989, 93, 7594.
200. Craw, J. S.; Hinchliffe, A.; Perez, J. J. In Self-Consistent Field: Theory and Applications, Carbó, R., Klobukowski, M., Eds.; Elsevier: Amsterdam, 1990; p 866 and references therein.
201. Hills, G. W.; Jones, W. J. J. Chem. Soc., Faraday Trans. 2 1975, 71, 812.
202. de Pascual-Teresa, B.; Houk, K. N. Tetrahedron Lett. 1996, 37, 1759.
203. For a recent report on the competition of concerted and stepwise mechanisms of various pericyclic reactions, see ref 21f.