Organolanthanide-mediated intermolecular hydroamination of 1,3-dienes: Mechanistic insights from a computational exploration of diverse mechanistic pathways for the stereoselective hydroamination of 1,3-butadiene with a primary amine supported by an ansa-neodymocene-based catalyst

Chemistry - A European Journal

Volumn 11, Issue 21, 2005, Pages 6372-6385

  Tobisch, Sven ^a  

^a MARTIN LUTHER UNIVERSITY HALLE WITTENBERG   (Germany)

Author keywords

Density functional calculations; Hydroamination; Lanthanides; Reaction mechanisms; Regio selectivity

Indexed keywords

AMINES; BUTADIENE; CATALYSTS; CHEMICAL BONDS; DATA ACQUISITION; FREE ENERGY; RARE EARTH ELEMENTS; REACTION KINETICS;

DENSITY FUNCTIONAL CALCULATIONS; HYDROAMINATION; REACTION MECHANISMS; REGIO-SELECTIVITY;

AMINATION;

EID: 27344448445     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200500355     Document Type: Article

References (134)

1. For reviews of catalytic hydroamination, see a) R. Taube in Applied Homogeneous Catalysis with Organometallic Complexes (Eds.: B. Cornils, W. A. Herrmann), Wiley-VCH, Weinheim, 1996, pp. 507-520;
2. b) L. S. Hegedus, Angew. Chem. 1988, 100, 1147;
3. Angew. Chem. Int. Ed. Engl. 1988, 27, 1113;
4. c) D. M. Roundhill, Catal. Today 1997, 37, 155;
5. d) T. E. Müller, M. Beller, Chem. Rev. 1998, 98, 675;
6. e) J. J. Brunet, D. Neibecker in Catalytic Heterofunctionalization (Eds.: A. Togni, H. Grützmacher), Wiley-VCH, Weinheim, 2001, pp. 91-141;
7. f) M. Nobis, B. Drießen-Höscher, Angew. Chem. 2001, 113, 4105;
8. Angew. Chem. Int. Ed. 2001, 40, 3983;
9. g) F. Pohlki, S. Doye, Chem. Soc. Rev. 2003, 32, 104;
10. h) P. W. Roesky, T. E. Müller, Angew. Chem. 2003, 115, 2812;
11. Angew. Chem. Int. Ed. 2003, 42, 2708;
12. i) J. F. Hartwig, Pure Appl. Chem. 2004, 76, 507.
13. For hydroamination mediated by early transition metals, see: a) P. L. McGrane, M. Jensen, T. Livinghouse, J. Am. Chem. Soc. 1992, 114, 5459;
14. b) P. L. McGrane, T. Livinghouse, J. Org. Chem. 1992, 57, 1323;
15. c)P. L. McGrane, T. Livinghouse, J. Am. Chem. Soc. 1993, 115, 11 485;
16. d) D. Fairfax, M. Stein, T. Livinghouse, M. Jensen, Organometallics 1997, 16, 1523;
17. e) F. Pohlki, S. Doye, Angew. Chem. 2001, 113, 2361;
18. Angew. Chem. Int. Ed. 2001, 40, 2305;
19. f) J. S. Johnson. R. G. Bergmann, J. Am. Chem. Soc. 2001, 123, 2923;
20. g) C. Cao, J. T. Ciszewski, A. L. Odom, Organometallics 2001, 20, 5011;
21. h) L. Ackermann, R. G. Bergmann, Org. Lett. 2002, 4, 1475;
22. i) T.-G. Ong, G. P. A. Yap, D. S. Richeson, Organometallics 2002, 21, 2839;
23. j) A. Tillack, I. G. Castro, C. G. Hartung, M. Beller, Angew. Chem. 2002, 114, 2646;
24. Angew. Chem. Int. Ed. 2002, 41, 2541;
25. k) Y. Shi, C. Hall, J. T. Ciszewski, C. Cao, A. L. Odom, Chem. Commun. 2003, 586.
26. For hydroamination mediated by late transition metals, see: a) T. E. Müller, M. Grosche, E. Herdtweck, A.-K. Pleier, E. Walter, Y.-K. Yan, Organometallics 2000, 19, 170;
27. b) D. Vasen, A. Salzer, F. Gerhards, H.-J. Gais, R. Stürmer, N. H. Bieler, A. Togni, Organometallics 2000, 19, 539;
28. c) M. Kawatsura, J. F. Hartwig, Organometallics 2001, 20, 1960;
29. d) T. E. Müller, M. Berger, M. Grosche, E. Herdtweck, F. P. Schmidtchen, Organometallics 2001, 20, 4384;
30. e) C. G. Hartung, A. Tillack, H. Trauthwein, M. Beller, J. Org. Chem. 2001, 66, 6339;
31. f) U. Nettekoven, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 1166;
32. g) V. Neff, T.E. Müller, J. A. Lecher, Chem. Commun. 2002, 906;
33. h) L. Fadini, A. Togni, Chem. Commun. 2003, 30.
34. For hydroamination mediated by rare earth metals, see: a) M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108;
35. b) M. R. Gagné, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275;
36. c) Y Li, T. J. Marks, J. Am. Chem. Soc. 1996, 118, 9295;
37. d) G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983;
38. e) Y. Li, T. J. Marks, J. Am. Chem. Soc. 1998, 120, 1757;
39. f) V. M. Arredondo, F. E. McDonald, T. J. Marks, Organometallics 1999, 18, 1949;
40. g) V. M. Arredondo, S. Tian, F. E. McDonalds, T. J. Marks, J. Am. Chem. Soc. 1999, 121, 3633;
41. h) Y. K. Kim. T. Livinghouse, J. E. Bercaw, Tetrahedron Lett. 2001, 42, 2933;
42. i) Y. K. Kim, T. Livinghouse, Angew. Chem. 2002, 114, 3797;
43. Angew. Chem. Int. Ed. 2002, 41, 3645;
44. j) J. Wang, A. K. Dash, M. Kapon, J.-C. Berthet, M. Ephritikhine, M. S. Eisen, Chem. Eur. J. 2002, 8, 5384;
45. k) Y. K. Kim, T. Livinghouse, Y. Horino, J. Am. Chem. Soc. 2003, 125, 9560;
46. l) D. V. Gribkov, K. C. Hultzsch, F. Hampel, Chem. Eur. J. 2003, 9, 4796;
47. m) B. D. Stubbert, C. L. Stern, T. J. Marks, Organometallics 2003, 22, 4836;
48. n) J.-S. Ryu, T. J. Marks, F. E. McDonald, J. Org. Chem. 2004, 69, 1038;
49. o) F. Lauterwasser. P. G. Hayes, S. Bräse, W. E. Piers, L. L. Schafer, Organometallics 2004, 23, 2234;
50. p) K. C. Hultzsch, F. Hampel, T. Wagner, Organometallics 2004, 23, 2601.
51. For reviews on organolanthanides, see: a) T. J. Marks, R. D. Ernst in Comprehensive Organometallic Chemistry (Eds.: G. Wilkinson, F. G. A. Stone, E. W. Abel), Pergamon Press, Oxford, 1982, Chap. 21;
52. b) W. J. Evans, Adv. Organomet. Chem. 1985, 24, 131;
53. c) C. J. Schaverien, Adv. Organomet. Chem. 1994, 36, 283;
54. d) H. Schumann, J. A. Meese-Marktscheffel, L. Esser, Chem. Rev. 1995, 95, 865;
55. c) F. T. Edelmann in Comprehensive Organometallic Chemistry, Vol.4 (Eds.: G. Wilkinson. F. G. A. Stone, E. W. Abel), Pergamon Press, Oxford, 1995 Chap. 2;
56. f) M. N. Bochkarev, Chem. Rev. 2002, 102, 2089;
57. g) S. Arndt, J. Okuda, Chem. Rev. 2002, 102, 1953;
58. h) F. T. Edelmann, D. M. M. Freckmann, H. Schumann, Chem. Rev. 2002, 102, 1851;
59. i) H. C. Aspinall, Chem. Rev. 2002, 102, 1807.
60. For reviews on organolanthanide catalysis, see: a) G. Jeske, H. Lauke, H. Mauermann, H. Schumann, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 8111;
61. b) P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51;
62. c) H. J. Heeres, J. Renkema, M. Booji, A. Meetsma, J. H. Teuben, Organometallics 1988, 7, 2495;
63. d) G. A. Moland er, J. O. Hoberg, J. Org. Chem. 1992, 57, 3266;
64. e) P. J. Shapiro, W. D. Cotter, W. P. Schaefer, J. A. Lahinger, J. E. Bercaw, J. Am. Chem. Soc. 1994, 116, 4623;
65. f) P.-F. Fu, L. Brard, Y. Li, T. J. Marks, J. Am. Chem. Soc. 1995, 117, 7157;
66. g) F. T. Edelmann, Top. Curr. Chem. 1996, 179, 247;
67. h) G. A. Molander, Chemtracts: Org. Chem. 1988, 18, 237;
68. i) Topics in Organometallic Chemistry, Vol. 2 (Ed.: S. Kobayashi), Springer, Berlin, 1999;
69. j) Z. Hou, Y. Wakatsuki, Coord. Chem. Rev. 2002, 231, 1;
70. k) G. A. Molander, J. A. C. Romero, Chem. Rev. 2002, 102, 2161;
71. M. Shihasaki, N. Yoshikawa, Chem. Rev. 2002, 102, 2187;
72. m) J. Inanaga, H. Furuno, T. Hayano, Chem. Rev. 2002, 102, 2211.
73. S. Hong, T. J. Marks. Acc. Chem. Res. 2004, 37, 673.
74. a) S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886;
75. b) S. Hong, A. M. Kawaoka, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 15878;
76. c) S. Hong, S. Tian, M. V. Metz, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 14768.
77. a) Y. Li, T. J. Marks. Organometallics 1996, 15, 3770;
78. b) J.-S. Ryu, G. Y. Li, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 12584.
79. 1H NMR spectroscopy: detailed kinetics, however, were not reported.
80. [7, 9a,b]
81. a) M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2000, 122, 9546;
82. b) O. Löber, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2001, 123, 4366;
83. c) J. Pawlas, Y. Nakao, M. Kawatsura, J. F. Hartwig, J. Am. Chem. Soc. 2002, 124, 3669.
84. T. Minami, H. Okamoto, S. Ikeda, R. Tanaka, F. Ozawa, M. Yoshifuji, Angew. Chem. 2001, 113, 4633;
85. Angew. Chem. Int. Ed. 2001, 40, 4501.
86. For computational mechanistic studies on transition metal assisted intermolecular hydroamination, see: a) B. F. Straub, R. G. Bergman, Angew. Chem. 2001, 113, 4768;
87. Angew. Chem. Int. Ed. 2001, 40, 4632;
88. b) H. M. Senn, P. E. Blöchl, A. Togni, J. Am. Chem. Soc. 2000, 122, 4098.
89. 3-allylic structures in organo-f-element chemistry: a) G. Jeske, H. Lauke, H. Mauermann, P. N. Swepston, H. Schumann, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 8091;
90. b) E. Bunel, B. J. Burger, J. E. Bercaw, J. Am. Chem. Soc. 1988, 110, 976;
91. c) S. P. Nolan, D. Stern, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 7844;
92. d) W. J. Evans, T. A. Ulibarri, J. W. Ziller, J. Am. Chem. Soc. 1990, 112, 2314;
93. e) A. Scholz, A. Smola, J. Scholz, J. Löbel, H. Schumann, K.-H. Thiele, Angew. Chem. 1991, 103, 444;
94. Angew. Chem. Int. Ed. Engl. 1991, 30, 435;
95. f) W. J. Evans, R. A. Keyer, G. W. Rabe, D. K. Drummond, J. W. Ziller, Organometallics 1993, 12, 4664;
96. g) W. J. Evans, S. L. Gonzales, J. W. Ziller, J. Am. Chem. Soc. 1994, 116, 2600.
97. a) R. Taube, H. Windisch, F. Görlitz, H. Schumann, J. Organomet. Chem. 1993, 445, 85;
98. b) R. Taube, H. Windisch, J. Organomet. Chem. 1994, 472, 71;
99. c) R. Taube, St. Maiwald, J. Sieler. J Organomet. Chem. 1996, 513, 37;
100. d) R. Taube, H. Windisch, St. Maiwald, H. Hemling, H. Schumann, J. Organomet. Chem. 1996, 513, 49;
101. e) R. Taube, H. Windisch, H. Weissenborn, H. Hemling, H. Schumann, J. Organomet. Chem. 1997, 548, 229;
102. f) R. Taube, St. Maiwald, J. Sieler, J. Organomet. Chem. 2001, 621, 327.
103. 1[9b]
104. a) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165;
105. b) O. Treutler, R. Ahlrichs, J. Chem. Phys. 1995, 102, 346;
106. c) K. Eichkorn, O. Treutler, H. Öhm, M. Häser. R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652.
107. a) P. A. M. Dirac, Proc. Cambridge Philos. Soc. 1930, 26, 376;
108. h) J. C. Slater, Phys. Rev. 1951, 81, 385;
109. c) S. H. Vosko, L. Wilk, M. Nussiar, Can. J. Phys. 1980, 58, 1200;
110. d) A. D. Becke, Phys. Rev. 1988, A38, 3098;
111. e) J. P. Perdew, Phys. Rev. B 1986, 33, 8822;
112. J. P. Perdew, Phys. Rev. B 1986, 34, 7406.
113. See, for instance: a) S. Tobisch, Th. Nowak, H. Boegel, J. Organomet. Chem. 2001, 619, 24;
114. b) H. Heiber, O. Gropen, J. K. Laerdahl, O. Swang, U. Wahlgreen, Theor. Chem. Acc. 2003, 110, 118.
115. See, for instance: a) S. Tobisch, Chem. Eur. J. 2005, 11, 3113;
116. b) S. Tobisch, J. Am. Chem. Soc. 2005, 127, in press.
117. For further details, see www.struked.de.
118. -1 on the ΔH/ΔG surface.
119. Noteworthily, very similar energy profiles are also predicted for the trans-1,2 and cis-1,2 insertion pathways, which, however, does not have any mechanistic relevance, since these pathways remain almost entirely closed in the catalytic reaction course.
120. J. Lukas, P. W. N. M. van Leeuwen, H. C. Volger, A. P. Kouwenhoven, J. Organomet. Chem. 1973, 47, 163.
121. a) J. W. Faller, M. E. Thomsen, M. J. Mattina, J. Am. Chem. Soc. 1971, 93, 2642;
122. b) K. Vrieze, Fluxional Allyl Complexes in Dynamic Nuclear Magnetic Resonance Spectroscopy (Eds.: L. M. Jackmann, F. A. Cotton), Academic Press. New York, 1975.
123. S. Tobisch, R. Taube, Organometallics 1999, 18, 3045.
124. [14d]
125. -1 (ΔG, syn/anti-butenyl form) relative to the favorable isomers shown in Figure 4.
126. [7-9]
127. [9c].
128. tot) are given relative to the catalyst's resting state 3-AS, corrected by the respective number of reactant molecules.
129. J. H. Espenson, Chemical Kinetics and Reaction Mechanism, 2nd ed., McGraw-Hill, New York, 1995.
130. -3) were applied, which can reasonably be assumed for the kinetically highly mobile reactant association/dissociation.
131. [9a,b]
132. 1.
133. [29]
134. In the comparison of the energetics of alternative regioisomeric paths, the respective favorable stereochemical pathways were considered.