Mechanistic investigation of organolanthanide-mediated hydroamination of conjugated aminodienes: A comprehensive computational assessment of various routes for diene activation

Chemistry - A European Journal

Volumn 16, Issue 46, 2010, Pages 13814-13824

  Tobisch, Sven ^a  

^a UNIVERSITY OF ST ANDREWS   (United Kingdom)

Author keywords

density functional calculations; dienes; hydroamination; lanthanides; reaction mechanisms

Indexed keywords

ACTIVATION ANALYSIS; CATALYSTS; CHEMICAL ACTIVATION; DENSITY FUNCTIONAL THEORY; LANTHANUM COMPOUNDS; OLEFINS; RARE EARTH ELEMENTS;

DIENES; EMPIRICAL RATE LAW; HYDROAMINATIONS; INSERTION MECHANISM; INTRAMOLECULAR HYDROAMINATION; MECHANISTIC ANALYSIS; MECHANISTIC STUDIES; REACTION MECHANISM;

AMINATION;

EID: 78649913033     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201001358     Document Type: Article

References (138)

1. For reviews of catalytic hydroamination, see
2. L. S. Hegedus, Angew. Chem. 1988, 100, 1147
3. Angew. Chem. Int. Ed. 1998, 37, 1113
4. D. M. Roundhill, Catal. Today 1997, 37, 155
5. T. E. Müller, M. Beller, Chem. Rev. 1988, 88, 675
6. M. Nobis, B. Drießen-Hölscher, Angew. Chem. 2001, 113, 4105
7. Angew. Chem. Int. Ed. 2001, 40, 3983
8. R. Taube, in Applied Homogeneous Catalysis with Organometallic Complexes (Eds.:, B. Cornils, W. A. Herrmann,), Wiley-VCH, Weinheim, 2002, pp. 513-524
9. F. Seayad, A. Tillack, C. G. Hartung, M. Beller, Adv. Synth. Catal. 2002, 344, 795
10. G. A. Molander, J. A. C. Romero, Chem. Rev. 2002, 102, 2161
11. F. Pohlki, S. Doye, Chem. Soc. Rev. 2003, 32, 104
12. P. W. Roesky, T. E. Müller, Angew. Chem. 2003, 115, 2812
13. Angew. Chem. Int. Ed. 2003, 42, 2708
14. J. F. Hartwig, Pure Appl. Chem. 2004, 76, 507
15. S. Hong, T. J. Marks, Acc. Chem. Res. 2004, 37, 673
16. K. C. Hultzsch, Adv. Synth. Catal. 2005, 347, 367
17. A. L. Odom, Dalton Trans. 2005, 225
18. R. Severin, S. Doye, Chem. Soc. Rev. 2007, 36, 1407
19. I. Aillaud, J. Collin, J. Hannedouche, E. Schulz, Dalton Trans. 2007, 5105
20. J. F. Hartwig, Nature 2008, 455, 314
21. T. E. Müller, K. C. Hultzsch, M. Yus, F. Foubelo, M. Tada, Chem. Rev. 2008, 108, 3795.
22. For cyclohydroamination mediated by organolanthanides, see
23. M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 4108
24. M. R. Gagné, T. J. Marks, J. Am. Chem. Soc. 1992, 114, 275
25. Y. Li, P.-F. Fu, T. J. Marks, Organometallics 1994, 13, 439
26. Y. Li, T. J. Marks, J. Am. Chem. Soc. 1996, 118, 9295
27. G. A. Molander, E. D. Dowdy, J. Org. Chem. 1998, 63, 8983
28. M. R. Bürgstein, H. Berberich, P. W. Roesky, Organometallics 1998, 17, 1452
29. V. M. Arredondo, F. E. McDonald, T. J. Marks, Organometallics 1999, 18, 1949
30. A. T. Gilbert, B. L. Davis, T. J. Emge, R. D. Broene, Organometallics 1999, 18, 2125
31. G. A. Molander, E. D. Dowdy, J. Org. Chem. 1999, 64, 6515
32. Y. K. Kim, T. Livinghouse, J. E. Bercaw, Tetrahedron Lett. 2001, 42, 2944
33. G. A. Molander, E. D. Dowdy, S. K. Pack, J. Org. Chem. 2001, 66, 4344
34. M. R. Bürgstein, H. Berberich, P. W. Roesky, Chem. Eur. J. 2001, 7, 3078
35. S. Hong, T. J. Marks, J. Am. Chem. Soc. 2002, 124, 7886
36. S. Hong, S. Tian, M. V. Metz, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 14768
37. A. Zulys, T. K. Panda, M. T. Gamer, P. W. Roesky, Chem. Commun. 2004, 2584
38. J.-S. Ryu, T. J. Marks, F. E. McDonald, J. Org. Chem. 2004, 69, 1038
39. A. M. Seyam, B. D. Stubbert, T. R. Jensen, J. J. O'Donnell III, C. L. Stern, T. J. Marks, Inorg. Chim. Acta 2004, 357, 4029
40. J. Collin, J.-C. Daran, O. Jacquet, E. Schulz, A. Trifonov, Chem. Eur. J. 2005, 11, 3455.
41. For some leading references, see
42. A. L. Casalnuovo, J. C. Calabrese, D. Milstein, Inorg. Chem. 1987, 26, 971
43. T. E. Müller, A.-K. Pleier, J. Chem. Soc. Dalton Trans. 1999, 583
44. T. E. Müller, M. Grosche, E. Herdtweck, A.-K. Pleier, E. Walter, Y.-K. Yan, Organometallics 2000, 19, 170
45. T. Kondo, T. Okada, T. Suzuki, T. Mitsudo, J. Organomet. Chem. 2001, 622, 149
46. S. Burling, L. D. Field, B. A. Messerle, P. Turner, Organometallics 2004, 23, 1714
47. L. M. Lutete, I. Kadota, Y. Yamamoto, J. Am. Chem. Soc. 2004, 126, 1622
48. L. D. Field, B. A. Messerle, K. Q. Vuong, P. Turner, Organometallics 2005, 24, 4241
49. G. B. Bajracharya, Z. Huo, Y. Yamamoto, J. Org. Chem. 2005, 70, 4883
50. Ch. F. Bender, R. A. Widenhoefer, J. Am. Chem. Soc. 2005, 127, 1070
51. D. Karshtedt, A. T. Bell, T. D. Tilley, J. Am. Chem. Soc. 2005, 127, 12640
52. X. Li, A. R. Chianese, T. Vogel, R. H. Crabtree, Org. Lett. 2005, 7, 5437
53. F. E. Michael, B. M. Cochran, J. Am. Chem. Soc. 2006, 128, 4246
54. A. Takemiya, J. F. Hartwig, J. Am. Chem. Soc. 2006, 128, 6042
55. N. T. Patil, L. M. Lutete, H. Wu, N. K. Pahadi, I. D. Gridnev, Y. Yamamoto, J. Org. Chem. 2006, 71, 4270
56. J. Zhou, J. F. Hartwig, J. Am. Chem. Soc. 2008, 130, 12220
57. J. L. McBee, A. T. Bell, T. D. Tilley, J. Am. Chem. Soc. 2008, 130, 16562
58. C. Munro-Leighton, S. A. Delp, N. M. Alsop, E. D. Blue, T. B. Gunnoe, Chem. Commun. 2008, 111
59. B. M. Cochran, F. E. Michael, J. Am. Chem. Soc. 2008, 130, 2786.
60. For computational studies of organolanthanide-assisted intramolecular HA of various substrate classes, see: aminoalkene substrates
61. A. Motta, G. Lanza, I. L. Fragala, T. J. Marks, Organometallics 2004, 23, 4097; aminoalkyne substrates
62. A. Motta, G. Lanza, I. L. Fragala, T. J. Marks, Organometallics 2006, 25, 5533; aminoallene substrate
63. S. Tobisch, Chem. Eur. J. 2006, 12, 2520; aminodiene substrates
64. S. Tobisch, J. Am. Chem. Soc. 2005, 127, 11979
65. S. Tobisch, Chem. Eur. J. 2007, 13, 9127.
66. L. E. Allan, D. J. Fox, R. J. Deeth, A. L. Gott, P. Scott, Proceedings of the 42nd IUPAC Congress, Glasgow, UK, August 2-7, 2009.
67. A possible explanation for the observed KIE in aminoalkene HA in the context of the La-N σ-bond insertive mechanism with turnover-limiting cyclisation is given in reference [2b]. Note that the rate-limiting step of the insertive mechanism is not identical for the various substrate classes; cyclisation is the rate-limiting event for aminoalkenes/-alkynes (ref. [4a,b]), whereas for aminoallenes/-dienes protonolysis is turnover limiting (ref. [4c,d])
68. S. Hong, A. M. Kawaoka, T. J. Marks, J. Am. Chem. Soc. 2003, 125, 15878
69. -1 (RT); reference [7a]; see also references [2n and 2m].
70. P. A. Hunt, Dalton Trans. 2007, 1743.
71. For computational studies of Group 4 transition-metal-assisted intramolecular HA of various substrate classes, see: aminoalkene substrates
72. C. Müller, R. Koch, S. Doye, Chem. Eur. J. 2008, 14, 10430; aminoallene substrates
73. S. Tobisch, Dalton Trans. 2006, 4277
74. S. Tobisch, Chem. Eur. J. 2007, 13, 4884
75. S. Tobisch, Chem. Eur. J. 2008, 14, 8590.
76. For computational studies of transition metal- and organolanthanide- assisted intermolecular HA, see
77. H. M. Senn, P. E. Blöchl, A. Togni, J. Am. Chem. Soc. 2000, 122, 4098
78. B. F. Straub, R. G. Bergman, Angew. Chem. 2001, 113, 4768
79. Angew. Chem. Int. Ed. 2001, 40, 4632
80. S. Tobisch, Chem. Eur. J. 2005, 11, 6372
81. C. A. Tsipis, C. E. Kefalidis, J. Organomet. Chem. 2007, 692, 5245.
82. For a computational study of organoactinide-assisted intramolecular HA of aminodienes see:, S. Tobisch, Chem. Eur. J. 2010, 16, 3441.
83. For a computational study of late transition-metal assisted HA of aminoalkenes, see:, K. D. Hesp, S. Tobisch, M. Stradiotto, J. Am. Chem. Soc. 2010, 132, 413.
84. The data presented herein for the lanthanocene-amido catalyst species and relevant steps of the Ln-N σ-bond insertive mechanism can deviate somewhat from the ones reported in reference [4d] on the identical catalyst system, which used a different (BP86) DFT method. The present study can be regarded as being superior, because of the applied state-of-the-art methodology that involves a more consistent treatment of the authentic reaction conditions, together with the usage of the modern, almost nonempirical, well-performing meta-GGA TPSS functional, as detailed in the computational methodology section.
85. The notation of key structures has been chosen according to reference [4d].
86. Substrate association and dissociation steps are known to be facile in organolanthanide-mediated intramolecular hydroamination. For NMR evidence of rapid association/dissociation of free amine and of amido/amine permutation see reference [2b].
87. See the Supporting Information for more detail.
88. 2La-amidodiene-substrate] form 3 t -S1 of the La-amido catalyst complex (with the appropriate number of substrate molecules) has been chosen as reference for relative free energies.
89. Only the most accessible pathways are shown; see the SI for a complete account of all the studied pathways.
90. 2La backbone are omitted for the sake of clarity. Note that the amino-/amidodiene units are displayed in a truncated fashion for several of the species.
91. 8, but a tentative structure for 3 t -S2 → 6 a -S1 transformation in a single step. Notably, the corresponding TS structure could not be located (see the text).
92. 3-allylic structures in organo-4f-element chemistry; see for instance
93. G. Jeske, H. Lauke, H. Mauermann, P. N. Swepston, H. Schumann, T. J. Marks, J. Am. Chem. Soc. 1985, 107, 8091
94. E. Bunell, B. J. Burger, J. E. Bercaw, J. Am. Chem. Soc. 1988, 110, 976
95. S. P. Nolan, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1989, 111, 7844
96. W. J. Evans, T. A. Ulibarri, J. W. Ziller, J. Am. Chem. Soc. 1990, 112, 2314
97. A. Scholz, A. Smola, J. Scholz, J. Löbel, H. Schimann, K.-H. Thiele, Angew. Chem. 1991, 103, 444
98. Angew. Chem. Int. Ed. Engl. 1991, 30, 435
99. R. Taube, H. Windisch, F. Görlitz, H. Schumann, J. Organomet. Chem. 1993, 445, 85
100. W. J. Evans, R. A. Keyer, G. W. Rabe, D. K. Drummond, J. W. Ziller, Organometallics 1993, 12, 4664
101. W. J. Evans, S. L. Gonzales, J. W. Ziller, J. Am. Chem. Soc. 1994, 116, 2600
102. R. Taube, H. Windisch, H. Hemling, H. Schumann, J. Organomet. Chem. 1998, 555, 201
103. R. Taube, St. Maiwald, J. Sieler, J. Organomet. Chem. 2001, 621, 327.
104. M. R. Gagné, L. Brard, V. P. Conticello, M. A. Giardello, C. L. Stern, T. J. Marks, Organometallics 1992, 11, 2003
105. M. A. Giardello, V. P. Conticello, L. Brard, M. Sabat, A. L. Rheingold, C. L. Stern, T. J. Marks, J. Am. Chem. Soc. 1994, 116, 10212
106. M. R. Douglass, M. Ogasawa, S. Hong, M. V. Metz, T. J. Marks, Organometallics 2002, 21, 283.
107. J. Lukas, P. W. N. M. van Leeuwen, H. C. Volger, A. P. Kouwenhoven, J. Organomet. Chem. 1973, 47, 153.
108. J. W. Faller, M. E. Thomsen, M. J. Mattina, J. Am. Chem. Soc. 1971, 93, 2642
109. K. Vrieze, Fluxional Allyl Complexes in Dynamic Nuclear Magnetic Resonance Spectroscopy (Eds.:, L. Jackmann, F. A. Cotton,), Academic Press, New York, 1975.
110. S. Tobisch, R. Taube, Organometallics 1999, 18, 3045.
111. R. Taube, H. Windisch, J. Organomet. Chem. 1994, 472, 71
112. R. Taube, H. Windisch, St. Maiwald, H. Hemling, H. Schuhmann, J. Organomet. Chem. 1996, 513, 49.
113. -1.
114. Examination by a linear-transit approach gave no indication that this process is associated with a significant enthalpy barrier.
115. -1 (Figure 7) for the most accessible pathways of the selectivity-determining and turnover-limiting aminolysis that leads to P6 a / P6 b / P6 c corresponds to a P6 a: P6 b: P6 c ratio of 98:2:0 (298.15 K) upon application of Stefan-Boltzmann statistics. A more detailed analysis can be found in reference [4d].
116. R. G. Parr, W. Yang, Density-Functional Theory of Atoms and Molecules, Oxford University Press, New York, 1989.
117. R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165
118. O. Treutler, R. Ahlrichs, J. Chem. Phys. 1995, 102, 346
119. TURBOMOLE, version 5.9, R. Ahlrichs, F. Furche, C. Hättig, W. Klopper, M. Sierka, F. Weigend, University of Karlsruh, Karlsruhe (Germany), 2006,.
120. P. A. M. Dirac, Proc. Royal Soc. London Ser. A 1929, 123, 714
121. J. C. Slater, Phys. Rev. 1951, 81, 385
122. J. P. Perdew, Y. Wang, Phys. Rev. B 1992, 45, 13244
123. J. Tao, J. P. Perdew, V. N. Staroverov, G. E. Scuseria, Phys. Rev. Lett. 2003, 91, 146401
124. J. P. Perdew, J. Tao, V. N. Staroverov, G. E. Scuseria, J. Chem. Phys. 2004, 120, 6898.
125. O. Vahtras, J. Almlöf, M. W. Feyereisen, Chem. Phys. Lett. 1993, 213, 514
126. K. Eichkorn, O. Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 242, 652.
127. M. Dolg, H. Stoll, A. Savin, H. Preuß, Theor. Chim. Acta 1989, 75, 173.
128. F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 2005, 7, 3297
129. F. Weigend, Phys. Chem. Chem. Phys. 2006, 8, 1057.
130. A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829
131. K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119.
132. A. Klamt, G. Schüürmann, J. Chem. Soc. Perkin Trans. 2 1993, 799
133. A. Klamt, in Encyclopedia of Computational Chemistry, Vol. 1 (Ed.:, P. Von R. Schleyer,), Wiley, New York, 1998, pp. 604-615.
134. K. B. Wiberg, Tetrahedron 1968, 24, 1083.
135. A. E. Reed, R. B. Weinstock, F. Weinhold, J. Chem. Phys. 1985, 83, 735.
136. NBO 4M, E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, F. Weinhold, Theoretical Chemistry Institute, University of Wisconsin, Madison, 1999.
137. ReSpect program, version 1.2, V. G. Malkin, O. L. Malkina, R. Reviakine, A. V. Arbuznikov, M. Kaupp, B. Schimmelpfennig, I. Malkin, M. Repiský, S. Komorovský, P. Hrobarik, E. Malkin, T. Helgaker, K. Ruud, 2005.
138. For further details, see:.