Organolanthanide-mediated intramolecular hydroamination/cyclization of conjugated aminodienes: A computational exploration of diverse mechanistic pathways for the regioselective generation of functionalized azacycles supported by a lanthanocene-based catalyst complex

Journal of the American Chemical Society

Volumn 127, Issue 34, 2005, Pages 11979-11988

  Tobisch, Sven ^a  

^a MARTIN LUTHER UNIVERSITY HALLE WITTENBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

DISSOCIATION; FREE ENERGY; KINETIC THEORY; THERMODYNAMICS;

DIENE INSERTION; EMPIRICAL RATE LAW; KINETIC FACTORS;

ORGANIC COMPOUNDS;

ALKADIENE; AMINE; LANTHANIDE;

AMINATION; ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION KINETICS; CHIRALITY; CYCLIZATION; DENSITY FUNCTIONAL THEORY; DISSOCIATION; PROTON TRANSPORT; REACTION ANALYSIS; STEREOCHEMISTRY; THERMODYNAMICS;

EID: 24144456560     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja042546h     Document Type: Article

References (118)

1. For reviews of catalytic hydroamination, see: (a) Hegedus, L. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 1113.
2. (b) Roundhill, D. M. Catal. Today 1997, 37, 155.
3. (c) Müller, T. E.; Beller, M. Chem. Rev. 1988, 88, 675.
4. (d) Brunei, J. J.; Neibecker, D. In Catalytic Heterofunctianalization; Togni, A., Grützmacher, H., Eds.; Wiley-VCH: Weinheim, 2001; pp 91-141.
5. (e) Nobis, M.; Driessen-Hölscher, B. Angew. Chem., Int. Ed. 2001, 40, 3983.
6. (f) Taube, R. In Applied Homogeneous Catalysis with Organometallic Complexes; Cornils, B., Herrmann, W. A., Eds.; Wiley-VCH: Weinheim, Germany, 2002; pp 513-524.
7. (g) Pohlki, F.; Doye, S. Chem. Soc. Rev. 2003, 32, 104.
8. For hydroamination mediated by early transition metals, see: (a) Pohlki, F.; Doye, S. Angew. Chem., Int. Ed. 2001, 40, 2305.
9. (b) Johnson, J. S.; Bergmann, R. G. J. Am. Chem. Soc. 2001, 123, 2923.
10. (c) Cao, C.; Ciszewski, J. T.; Odom, A. L. Organometallics 2001, 20, 5011.
11. (d) Straub, B. F.; Bergman, R. G. Angew. Chem., Int. Ed. 2001, 40, 4632.
12. (e) Ackermann, L.; Bergmann, R. G. Org. Lett. 2002, 4, 1475.
13. (f) Ong, T.-G.; Yap, G. P. A.; Richeson, D. S. Organometallics 2002, 21, 2839.
14. (g) Tillack, A.; Castro, I. G.; Hartung, C. G.; Beller, M. Angew. Chem., Int. Ed. 2002, 41, 2541.
15. (h) Shi, Y.; Hall, C.; Ciszewski, J. T.; Cao, C.; Odom, A. L. Chem. Commun. 2003, 586.
16. For hydroamination mediated by late transition metals, see: (a) Müller, T. E.; Grosche, M.; Herdtweck, E.; Pleier, A.-K.; Walter, E.; Yan, Y.-K. Organometallics 2000, 19, 170.
17. (b) Vasen, D.; Salzer, A.; Gerhards, F.; Gais, H.-J.; Stürmer, R.; Bieler, N. H.; Togni, A. Organometallics 2000, 19, 539.
18. (c) Kawatsura, M.; Hartwig, J. F. Organometallics 2001, 20, 1960.
19. (d) Müller, T. E.; Berger, M.; Grosche, M.; Herdtweck, E.; Schmidtchen, F. P. Organometallics 2001, 20, 4384.
20. (e) Hartwig, C. G.; Tillack, A.; Trauthwein, H.; Beller, M. J. Org. Chem. 2001, 66, 6339.
21. (f) Nettekoven, U.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 1166.
22. (g) Neff, V.; Müller, T. E.; Lecher, J. A. Chem. Commun. 2002, 906.
23. (h) Fadini, L.; Togni, A. Chem. Commun. 2003, 30.
24. For hydroamination mediated by rare earth metals, see: (a) Gagné, M. R.; Marks, T. J. J. Am. Chem. Soc. 1989, 111, 4108.
25. (b) Gagné, M. R.; Stern, C. L.; Marks. T. J. J. Am. Chem. Soc. 1992, 114, 275.
26. (c) Li, Y.; Marks, T. J. J. Am. them. Soc. 1996, 118, 9295.
27. (d) Molander. G. A.; Dowdy, E. D. J. Org. Chem. 1998, 63, 8983.
28. (e) Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1998, 120, 1757.
29. (f) Arredondo, V. M.; McDonald, F. E.; Marks, T. J. Organometallics 1999, 18, 1949.
30. (g) Arredondo, V. M.; Tian, S.; McDonalds, F. E.; Marks, T. J. J. Am. Chem. Soc. 1999, 121, 3633.
31. (h) Kim, Y. K.; Livinghouse, T.; Bercaw, J. E. Tetrahedron Lett. 2001, 42, 2933.
32. (i) Kim, Y. K.; Livinghouse, T. Angew. Chem., Int. Ed. 2002, 41, 3645.
33. (j) Wang, J.; Dash, A. K.; Kapon, M.; Berthet, J.-C.; Ephritikhine, M.; Eisen, M. S. Chem. Eur. J. 2002, 8, 5384.
34. (k) Kim, Y. K.; Livinghouse, T.; Horino, Y. J. Am. Chem. Soc. 2003, 125, 9560.
35. (l) Gribkov, D. V.; Hultzsch, K. C.; Hampel, F. Chem. Eur. J. 2003, 9, 4796.
36. (m) Stubbert, B. D.; Stern, C. L.; Marks, T. J. Organometallics 2003, 22, 4836.
37. (n) Ryu, J.-S.; Marks, T. J.; McDonald, F. E. J. Org. Chem. 2004, 69, 1038.
38. For organolanthanide reviews, see: (a) Marks, T. J.; Ernst, R. D. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, U.K., 1982; Chapter 21.
39. (b) Evans, W. J. Adv. Organomet. Chem. 1985, 24, 131.
40. (c) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283.
41. (d) Schumann, H.; Meese-Marktscheffel, J. A.; Esser, L. Chem. Rev. 1995, 95, 865.
42. (e) Edelmann, F. T. In Comprehensive Organometallic Chemistry; Wilkinson, G., Stone, F. G. A., Abel, E. W., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol. 4, Chapter 2.
43. (f) Bochkarev, M. N. Chem. Rev. 2002, 102, 2089.
44. (g) Arndt, S.; Okuda, J. Chem. Rev. 2002, 102, 1953.
45. (h) Edelmann, F. T.; Freckmann, D. M. M.; Schumann. H. Chem. Rev. 2002, 102, 1851.
46. (i) Aspinall, H. C. Chem. Rev. 2002, 102, 1807.
47. For reviews on organolanthanide catalysis, see: (a) Jeske. G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111.
48. (b) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51.
49. (c) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495.
50. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266.
51. (e) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623.
52. (f) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157.
53. (g) Edelmann, F. T. Top. Curr. Chem. 1996, 179, 247.
54. (h) Molander, G. A. Chemtracts: Org. Chem. 1988, 18, 237.
55. (i) Topics in Organometallic Chemistrv; Kobayashi. S., Ed.; Springer: Berlin, Germany, 1999; Vol. 2.
56. (j) Hou, Z.; Wakatsuki, Y. Coord. Chem. Rev. 2002. 231, 1.
57. (k) Molander, G. A.; Romero, J. A. C. Chem. Rev. 2002, 102, 2161.
58. (l) Shibasaki, M.; Yoshikawa, N. Chem. Rev. 2002, 102, 2187.
59. (m) Inanaga, J.; Furuno, H.; Hayano, T. Chem. Rev. 2002, 102, 2211.
60. Hong, S.; Marks. T. J. Acc. Chem. Rex. 2004, 37, 673.
61. (a) Hong, S.; Marks, T. J. J. Am. Chem. Soc. 2002, 124, 7886.
62. (b) Hong, S.; Kawaoka, A. M.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 15878.
63. (c) Hong, S.; Tian, S.; Metz, M. V.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 14768.
64. ≠ = -32.7 eu; ref 8b)
65. (a) Li, Y.; Marks, T. J. Organometallics 1996, 15, 3770.
66. (b) Ryu, J.-S.; Li, G. Y.; Marks, T. J. J. Am. Chem. Soc. 2003, 125, 12584.
67. (a) Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 2000, 122, 9546.
68. (b) Löber, O.; Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 2001, 123, 4366.
69. (c) Pawlas, J.; Nakao, Y.; Kawatsura. M.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 3669.
70. Minami, T.; Okamoto, H.; Ikeda, S.; Tanaka, R.; Ozawa, F.; Yoshifuji, M. Angew. Chem., Int. Ed. 2001, 40, 4501.
71. (a) Motta, A.; Lanza, G.; Fragala, I. L.; Marks, T. J. Organometallics 2004, 23, 4097.
72. ≠ = -14.6 eu for intramolecular cyclization, therefore, do not relate to the intrinsic kinetics for this step either.
73. 3-allylic structures in organo-f-element chemistry; see: (a) Jeske, G.; Lauke, H.; Mauermann, H.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8091.
74. (b) Bunel, E.; Burger, B. J.; Bercaw, J. E. J. Am. Chem. Soc. 1988, 110, 976.
75. (c) Nolan, S. P.; Stern, D.; Marks, T. J. J. Am. Chem. Soc: 1989, 111, 7844.
76. (d) Evans, W. J.; Ulibarri, T. A.; Ziller, J. W. J. Am. Chem. Soc. 1990, 112, 2314.
77. (e) Scholz, A.; Smola, A.; Scholz, J.; Löbel, J.; Schimann, H.; Thiele, K.-H. Angew. Chem., Int. Ed. Engl. 1991, 30, 435.
78. (f) Evans, W. J.; Keyer, R. A.; Rabe, G. W.; Drummond, D. K.; Ziller, J. W. Organometallics 1993, 12, 4664.
79. (g) Evans, W. J.; Gonzales, S. E.; Ziller, J. W. J. Am. Chem. Soc. 1994, 116, 2600.
80. (a) Taube, R.; Windisch, H.; Görlitz, F.; Schumann, H. J. Organomet. Chem. 1993, 445, 85.
81. (b) Taube, R.; Windisch, H. J. Organomet. Chem. 1994, 472, 71.
82. (c) Taube, R.; Maiwald, St.; Sieler, J. J. Organomet. Chem. 1996, 513, 37.
83. (d) Taube, R.; Windisch, H.; Maiwald, St.; Hemling, H.; Schumann, H. J. Organomet. Chem. 1996, 513, 49.
84. (e) Taube, R.; Windisch, H.; Weissenborn, H.; Hemling, H.; Schumann, H. J. Organomet. Chem. 1997, 548, 229.
85. (f) Taube, R.; Windisch, H.; Hemling, H.; Schumann, H. J. Organomet. Chem. 1998, 555, 201.
86. (g) Taube, R.; Maiwald, St.; Sieler, J. J. Organomet. Chem. 2001, 621, 327.
87. (a) Ahlrichs, R.; Bär, M.; Häser, M.; Horn, H.; Kölmel, C. Chem. Phys. Lett. 1989, 162, 165.
88. (b) Treutler, O.; Ahlrichs, R. J. Chem. Phys. 1995, 102, 346.
89. (c) Eichkorn, K.; Treutler, O.; Öhm, H.; Häser, M.; Ahlrichs, R. Chem. Phys. Lett. 1995, 242, 652.
90. (a) Dirac, P. A. M. Proc. Cambridge Philos. Soc. 1930, 26, 376.
91. (b) Slater, J. C. Phys. Rev. 1951, 81, 385.
92. (c) Vosko, S. H.; Wilk, L.; Nussiar, M. Can. J. Phys. 1980, 58, 1200.
93. (d) Becke, A. D. Phys. Rev. 1988, A38, 3098.
94. (e) Perdew, J. P. Phys. Rev. 1986, B33, 8822;
95. Phys. Rev. B 1986, 34, 7406.
96. For instance, see: (a) Tobisch, S.; Nowak, Th.; Boegel, H. J. Organomet. Chem. 2001, 619, 24.
97. (b) Heiber, H.; Gropen, O.; Laerdahl, J. K.; Swang, O.; Wahlgreen, U. Theor. Chem. Acc. 2003, 110, 118.
98. Tobisch, S. Chem. Eur. J. 2005, 11, 3113.
99. For further details, see: www.struked.de.
100. For substrate adducts X-S, the -S(t) and -S(c) suffixes denotes the 4E(trans) and 4Z(cis) isomers of the heptadien-1-amine aminodiene substrate 1.
101. 10) × T × exp(-ΔG‡/RT).
102. For NMR evidence of rapid amido/amine permutation and association of free amine, see ref 4b.
103. 3)] compound (ref 4b).
104. Lukas, J.; van Leeuwen, P. W. N. M.; Volger, H. C.; Kouwenhoven, A. P. J. Organomet. Chem. 1973, 47, 163.
105. (a) Faller, J. W.; Thomsen, M. E.; Mattina, M. J. J. Am. Chem. Soc. 1971, 93, 2642.
106. (b) Vrieze, K. Fluxional Allyl Complexes. In Dynamic Nuclear Magnetic Resonance Spectroscopy, Jackmann, L. M., Cotton, F. A., Eds.; Academic Press: New York, 1975.
107. Tobisch, S.; Taube, R. Organometallics 1999, 18, 3045.
108. 3] dioxane adduct (ref 14d).
109. The examination by a linear transit approach revealed no indication that this process is connected with a significant enthalpic barrier.
110. Senn, H. M.; Blöchl, P. E.; Togni, A. J. Am. Chem. Soc. 2000, 122, 4098.
111. -1 by considering real reaction conditions (80 molar excess of S(t), 298.15 K, 1 atm).
112. tot) are given relative to the catalyst's resting state 3t′-S, corrected by the respective number of substrate molecules.
113. (a) Espensoll, J. H. Chemical Kinetics and Reaction Mechanisms, 2nd ed.; McGraw-Hill: New York, 1995.
114. (b) Compound 4s is likely to be a transient species, thus being present in negligible stationary concentrations, because its formation via reversible 3t″ → 4s cyclization and ensuing 4s + S(t) → 4s-S(t) substrate association are facile processes.
115. The rate law (eq 2) does also account for substrate self-inhibition effects that have been experimentally observed in octadienylamine cycloamination (ref 8b)
116. See Scheme S1 and S2, respectively, by taking the actual reaction conditions into account (ref 30).
117. It should be noted that the prediction of accurate entropies for lanthanide-as well as for transition-metal-assisted processes taking place in condensed phase remains still a frontier in computational chemistry.
118. -1.