Titanacyclobutane Synthesis by Radical Alkylation of Substituted Allyl Complexes. the Use of Electron-Rich Bis(2-piperidinoindenyl)titanocene(III) Complexes to Control Allyl Ligand Reactivity

Organometallics

Volumn 18, Issue 5, 1999, Pages 820-822

  Carter, Charles A G ^a,b   McDonald, Robert ^a,c   Stryker, Jeffrey M ^a  

^a UNIVERSITY OF ALBERTA   (Canada)

^b LOS ALAMOS NATIONAL LABORATORY   (United States)

^c Faculty Service Officer

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001606339     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980883r     Document Type: Article

References (37)

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2. (b) Ogoshi, S.; Stryker, J. M. J. Am. Chem. Soc. 1998, 120, 3514.
3. Carter, C. A. G.; Chen, J. X.; Greidanus, G.; Casty, G. L.; Noraura, N.; Stryker, J. M. Manuscript in preparation.
4. Costa, E. M.; Stryker, J. M. Unpublished results.
5. 1b Certain intramolecular radical alkylations using allyl substrates are also productive: Nomura, N.; Stryker, J. M. Unpublished results.
6. 3-coordinate: Luinstra, G. A.; ten Cate, L. C.; Heeres, H. J.; Pattiasina, J. W.; Meetsma, A.; Teuben, J. H. Organometallics 1991, 10, 3227.
7. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
8. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
9. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
10. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
11. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
12. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
13. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
14. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
15. 0-complexes are kinetically labile, undergoing rapid η,3 ↔ η1 equilibration. See: (a) Martin, H. A.; Lemaire, P. J.; Jellinek, F. J. Organomet. Chem. 1968, 14, 149. (b)Yasuda, H.; Kajihara, Y.; Mashima. K; Nagasuna, K.; Nakamura, A. Chem. Lett. 1981, 671. Mashima, K.; Yasuda, H.; Asami, K.; Nakamura, A. Chem. Lett. 1983, 219. Blenkers, J.; de Liefde Meijer, H. J.; Teuben, J. H. J. Organomet. Chem. 1981, 218, 383. McDade, C., Bercaw, J. E. J. Organomet. Chem. 1986, 279, 281. (e) Highcock, W. J.; Mills, R. M.; Spencer, J. L.; Woodward, P. J. Chem. Soc., Dalton Trans. 1986, 829, and references therein, (f) Larson, E. J.; van Dort, P. C.; Lakanen, J. R.; O'Neill, D. W.; Pederson, L. M.; McCandless, J. J.; Silver, M. E.; Russo, S. O.; Huffman, J. D. Organometallics 1988, 7, 1183. Vance, P. J.; Prins, T. J.; Hauger, B. E.; Silver, M. E.; Wemple, M. E.; Pederson, L. M.; Kort, D. A.; Kannisto, M. R.; Geerligs, S. J.; Kelly, R. S.; McCandless, J. J.; Huffman, J. D.; Peters, D. G. Organometallics 1991, 10, 917. (g) Tjaden, E. B.; Stryker, J. M. J. Am. Chem. Soc. 1993, 115, 2083.
16. 3-allyltitanocene complexes: Lauher, J. W.; Hoffman, R. J. Am. Chem. Soc. 1976, 98, 1729. Curtis, M. D.; Eisenstein, O. Organometallics 1984, 3, 887.
17. 3-allyltitanocene complexes: Lauher, J. W.; Hoffman, R. J. Am. Chem. Soc. 1976, 98, 1729. Curtis, M. D.; Eisenstein, O. Organometallics 1984, 3, 887.
18. (a) Casty, G. L. Ph.D Dissertation, Indiana University, 1994.
19. (b) Carter, C. A. G. Ph.D. Dissertation, University of Alberta, 1998.
20. (a) Stahl, K.-P.; Boche, G. Massa, J. Organomet. Chem. 1984, 277, 113.
21. (b) Plenio, H.; Burth, D. J. Organomet. Chem. 1996, 519, 269.
22. Barsties, E.; Schaible, S.; Prosenc, M.-H.; Rief, U.; Röll, W.; Weyand, O.; Dorer, B.; Brintzinger, H.-H. J. Organomet. Chem. 1996, 520, 63.
23. Luttikhedde, H. J. G.; Leino, R. P.; Wilén, C.-E.; Näsman, J. H.; Ahlgrén, M. J.; Pakkanen, T. A. Organometallics 1996, 15, 3092.
24. Complete experimental, spectroscopic, and analytical data are provided as Supporting Information.
25. Blomquist, A. T.; Moriconi, E. J. J. Org. Chem. 1961, 26, 3761. Treibs, von W.; Schroth. W. Justus Liebigs Ann. Chem. 1961, 639, 204.
26. Blomquist, A. T.; Moriconi, E. J. J. Org. Chem. 1961, 26, 3761. Treibs, von W.; Schroth. W. Justus Liebigs Ann. Chem. 1961, 639, 204.
27. 2: C, 79 13; H, 7.36; N, 4.99. Found: C, 78.79; H, 7.51; N, 4.94.
28. Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem. Soc. 1980, 102, 2693.
29. 2O: C. 77.85; H, 8.61; N, 4.13. Found: C, 77.74; H, 8.24; N, 4.57
30. 10 a result most consistent with placing the phenyl substituent cis to the β-hydrogen and trans to the isopropyl group).
31. 1H NMR spectroscopy and GC-MS. The organic decomposition products presumably arise from β-hydride elimination at the a-methyl substituent, followed by reductive elimination. In contrast, cinnamyl-derived complex 4c decomposes by [2 + 2] cycloreversion at elevated temperatures (<80°C), giving 3,3-dimethylbutene as the exclusive organic product.
32. 2), -0.24 (m, 1H, βCH).
33. 2).10
34. Other structurally characterized titanocene allyl complexes: (a) Helmholdt, R. B.; Jellinek, F.; Martin, H. A.; Vos, A. Recl. Trav. Chim. Pays-Bas 1967, 86, 1263. (b) Chen, J.; Kai, Y.; Kasai, N.; Yasuda, H.; Yamamoto, H.; Nakamura, A. J. Organomet. Chem. 1991, 407, 191.
35. Other structurally characterized titanocene allyl complexes: (a) Helmholdt, R. B.; Jellinek, F.; Martin, H. A.; Vos, A. Recl. Trav. Chim. Pays-Bas 1967, 86, 1263. (b) Chen, J.; Kai, Y.; Kasai, N.; Yasuda, H.; Yamamoto, H.; Nakamura, A. J. Organomet. Chem. 1991, 407, 191.
36. 9c,d (21) Torsion angles (deg): C19-N1-C10-C11 = -14.6(9), C19N1-C10-C18= 171.8(6), C23-N1-C10-C11 = -150.2(6), C23-N1C10-C18 = 36.2(9); C39-N2-C30-C31 = 2.8(8), C39-N2-C30-C38 = -177.6(6), C43-N2-C30-C31 = -124.9(6), C43-N2-C30-C38 = 54.7(7).
37. 10 While such distortions can certainly arise from intermolecular crystal packing forces, there is nothing obvious in the extended structure to suggest that this is the case.