Synthesis of [Ethylene-1-(η 5-4,5,6,7-tetrahydro-1-indenyl)-2-(η5-4′ ,5′,6′,7′-tetrahydro-2′-indenyl)]titanium Dichloride, the Elusive Isomer of the Brintzinger-Type ansa-Titanocenes

Journal of Organic Chemistry

Volumn 68, Issue 22, 2003, Pages 8447-8452

  Kelly, Patrick A ^a   Berger, Gideon O ^a   Wyat, Justin K ^b   Nantz, Michael H ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b School of Business   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYLATION; COMPLEXATION; HYDROGENATION; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

SYNTHETIC STRATEGY;

ORGANIC COMPOUNDS;

1 (2 INDENYL) 2 (3 INDENYL)ETHANE; 2 (PHENYLSULFONYL)INDANE; [ETHYLENE 1 (4,5,6,7 TETRAHYDRO 1 INDENYL) 2 (4',5',6',7' TETRAHYDRO 2' INDENYL)]TITANIUM DICHLORIDE; HEMPA; INDAN DERIVATIVE; INDENE DERIVATIVE; TITANOCENE; UNCLASSIFIED DRUG;

ARTICLE; COMPLEX FORMATION; HYDROGENATION; ISOMER; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

EID: 0142227981     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo034975o     Document Type: Article

References (53)

1. (a) Organometallic Complexes and Olefin Polymerization; Blom, R., Follestad, A., Rytter, E., Tilset, M., Ystenes, M., Eds.; Springer: Berlin, Germany, 2001.
2. (b) Halterman, R. L. In Metallocenes; Togni, A., Halterman, R. L., Eds.; Wiley-VCH: New York, 1998; pp 455-544.
3. (c) Kaminsky, W. J. Chem. Soc., Dalton Trans. 1998, 1413.
4. (d) Brintzinger, H. H.; Fischer, D.; Mülhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143.
5. (a) Yun, J.; Buchwald, S. L. J. Org. Chem. 2000, 65, 767.
6. (b) Troutman, M. V.; Appella, D. H.; Buchwald, S. L. J. Am. Chem Soc. 1999, 121, 4916.
7. (c) Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1999, 121, 7026.
8. (d) Catalytic Enantioselective Alkylation of Alkenes by Chiral Metallocenes; Beller, M., Bolm, C., Eds.; Wiley-VCH: Weinheim, Germany, 1998.
9. (e) Hoveyda, A. H.; Morken, J. P. Angew. Chem., Int. Ed. Engl. 1996, 35, 1263.
10. (f) Duthaler, R. O.; Hafner, A. Chem. Rev. 1992, 92, 807.
11. (g) Willoughby, C. A.; Buchwald, S. L. J. Am. Chem. Soc. 1992, 114, 7562.
12. (h) Hollis, T. K.; Robinson, N. P.; Bosnich, B. Tetrahedron Lett. 1992, 43, 6423.
13. (i) Grossman, R. B.; Davis, W. M.; Buchwald, S. L. J. Am. Chem. Soc. 1991, 113, 2321.
14. Shapiro, P. J. Coord. Chem. Rev. 2002, 231, 67.
15. Wild, F. R. W. P.; Zsolnai, L.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1982, 232, 233.
16. (a) Schäfer, A.; Karl, E.; Zsolnai, L.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1987, 328, 87.
17. (b) Collins, S.; Kuntz, B. A.; Taylor, N. J.; Ward, D. G. J. Organomet. Chem. 1988, 342, 21.
18. (c) Collins, S.; Kuntz, B. A.; Hong, Y. J. Org. Chem. 1989, 54, 4154.
19. (d) Grossman, R. B.; Doyle, R. A.; Buchwald, S. L. Organometallics 1991, 10, 1501.
20. The corresponding enantioenriched titanocene difluoride, and the titanocene and zirconocene binaphthyl-2,2′-diolates are available commercially.
21. (a) Nantz, M. H.; Hitchcock, S. R.; Sutton, S. C.; Smith, M. D. Organometallics 1993, 12, 5012.
22. (b) Hitchcock, S. R.; Situ, J. J.; Covel, J. A.; Olmstead, M. M.; Nantz, M. H. Organometallics 1995, 14, 3732.
23. Sugie, A.; Shimomura, H.; Katsube, J.; Yamamoto, H. Tetrahedron Lett. 1977, 18, 2759.
24. (a) Palandoken, H.; McMillen, W. T.; Nantz, M. H. Org. Prep. Proc. Intl. 1996, 28 702.
25. (b) Palandoken, H.; Wyatt, J. K.; Hitchcock, S. R.; Olmstead, M. M.; Nantz, M. H. J. Organomet. Chem. 1999, 579, 338.
26. Several strategies have been reported for substitution of indene at the 2-position; for examples, see: (a) Greifenstein, L. G.; Lambert, J. B.; Nienhuis, R. J.; Fried, H. E.; Pagani, G. A. J. Org. Chem. 1981, 46, 5125.
27. (b) Adamczyk, M.; Watt, D. S.; Netzel, D. A. J. Org. Chem. 1984, 49, 4226.
28. (c) Kaminsky, W.; Rabe, O.; Schauwienold, A. M.; Schupfner, G. U.; Hanss, J.; Kopf, J. J. Organomet. Chem. 1995, 497, 181.
29. (d) Halterman, R. L.; Zhu, C. Tetrahedron Lett. 1999, 40, 7445.
30. McCullough, K. J. Tetrahedron Lett. 1982, 23, 2223.
31. Trost, B. M.; Curran, D. P. Tetrahedron Lett. 1981, 22, 1287.
32. Kauffman, T.; Berghus, K.; Rensing, A. Chem. Ber. 1985, 118, 3737.
33. (a) Rheingold, A. L.; Robinson, N. P.; Whelan, J.; Bosnich, B. Organometallics 1992, 11 1869.
34. (b) Lee, I. M.; Gauthier, W. J.; Ball, J. M.; Iyengar, B.; Collins, S. Organometallics 1992, 11, 2115.
35. (c) Halterman, R. L.; Schumann, H.; Dübner, F. J. Organomet. Chem. 2000, 604, 12.
36. In similar fashion, 1,2-dibromoethane is reported to brominate an ester enolate anion, see: Greene, A. E.; Muller, J. C.; Ourisson, G. J. Org. Chem. 1974, 39, 186.
37. Achmatowicz, B.; Marczak, S.; Wicha, J. J. Chem. Soc., Chem. Commun. 1987, 1226.
38. 2O was added to i. The THF cleavage product ii was isolated on aqueous workup. For an analogous reaction with THF, see: Christoffers, J.; Dötz, K. H. Organometallics 1994, 13, 4189.
39. (a) Hollis, T. K.; Rheingold, A. L.; Robinson, N. P.; Whelan, J.; Bosnich, B. Organometallics 1992, 11, 2812.
40. (b) Sutton, S. C.; Nantz, M. H.; Parkin, S. R. Organometallics 1993, 12, 2248.
41. (c) Chen, Z.; Halterman, R. L. Organometallics 1994, 13, 3932.
42. (d) Shapiro, P. J.; Kane, K. M.; Vij, A.; Stelck, D.; Matare, G. J.; Hubbard, R. L.; Caron, B. Organometallics 1999, 18, 3468.
43. Singh, A. K.; Bakshi, R. K.; Corey, E. J. J. Am. Chem. Soc. 1987, 109, 6187.
44. Magnus, P. D. Tetrahedron 1977, 33, 2019.
45. Radisson, X.; Kwiatkowski, P. L.; Fuchs, P. L. Synth. Commun. 1987, 17, 39.
46. Manzer, L. E. Inorg. Synth. 1982, 21, 135.
47. Collins, S.; Hong, Y.; Taylor, N. J. Organometallics 1990, 9, 2695.
48. (a) Halterman, R. L.; Vollhardt, K. P. C. Organometallics 1988, 7, 883.
49. (b) Chen, Z.; Halterman, R. L. J. Am. Chem. Soc. 1992, 114, 2276.
50. Chen, Z. C.; Eriks, K.; Halterman, R. L. Organometallics 1991, 10, 3449.
51. (a) Diamond, G. M.; Rodewald, S.; Jordan, R. F. Organometallics 1995, 14, 5.
52. (b) Diamond, G. M.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1996, 118, 8024.
53. Emerging resonances at δ 5.84 (d, J = 2.4 Hz, 1H), 5.94 (d, J = 2. 6 Hz), 6.11 (d, J = 2.9 Hz), and 6.45 (d, J = 2.9 Hz, 1H) within 3 h suggest zirconocene formation.