Highly regioselective alkyne cyclotrimerization catalyzed by titanium complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands [6]

Journal of the American Chemical Society

Volumn 121, Issue 34, 1999, Pages 7941-7942

  Ozerov, Oleg V ^a   Ladipo, Folami T ^a   Patrick, Brian O ^a  

^a UNIVERSITY OF KENTUCKY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

5 TERT BUTYLCALIX[4]ARENE; ALKYNE; CALIXARENE; TITANIUM DERIVATIVE; UNCLASSIFIED DRUG;

CATALYST; COMPLEX FORMATION; LETTER; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033198652     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990740b     Document Type: Letter

References (43)

1. See, for example: (a) Ojima, I.; Tzamarioudaki, M.; Zhaoyang, L.; Donovan, R. J. Chem. Rev. 1996, 96, 635. (b) Negishi, E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Permagon: Oxford, 1991; Vol. 5, pp 1163-1184. (c) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539. (d) Schore, N. E. Chem. Rev. 1988, 88, 1081. (e) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1.
2. See, for example: (a) Ojima, I.; Tzamarioudaki, M.; Zhaoyang, L.; Donovan, R. J. Chem. Rev. 1996, 96, 635. (b) Negishi, E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Permagon: Oxford, 1991; Vol. 5, pp 1163-1184. (c) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539. (d) Schore, N. E. Chem. Rev. 1988, 88, 1081. (e) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1.
3. See, for example: (a) Ojima, I.; Tzamarioudaki, M.; Zhaoyang, L.; Donovan, R. J. Chem. Rev. 1996, 96, 635. (b) Negishi, E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Permagon: Oxford, 1991; Vol. 5, pp 1163-1184. (c) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539. (d) Schore, N. E. Chem. Rev. 1988, 88, 1081. (e) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1.
4. See, for example: (a) Ojima, I.; Tzamarioudaki, M.; Zhaoyang, L.; Donovan, R. J. Chem. Rev. 1996, 96, 635. (b) Negishi, E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Permagon: Oxford, 1991; Vol. 5, pp 1163-1184. (c) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539. (d) Schore, N. E. Chem. Rev. 1988, 88, 1081. (e) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1.
5. See, for example: (a) Ojima, I.; Tzamarioudaki, M.; Zhaoyang, L.; Donovan, R. J. Chem. Rev. 1996, 96, 635. (b) Negishi, E. In Comprehensive Organic Synthesis; Trost, B. M., Ed.; Permagon: Oxford, 1991; Vol. 5, pp 1163-1184. (c) Tamao, K.; Kobayashi, K.; Ito, Y. Synlett 1992, 539. (d) Schore, N. E. Chem. Rev. 1988, 88, 1081. (e) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1986, 25, 1.
6. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
7. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
8. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
9. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
10. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
11. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
12. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
13. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
14. See, for example: (a) McAllister, D. R.; Bercaw, J. E.; Bergman, R. G. J. Am. Chem. Soc. 1977, 99, 1666. (b) Volhardt, K. P. C. Angew. Chem., Int. Ed. Engl. 1984, 23, 539. (c) Strickler, J. R.; Bruck, M. A.; Wigley, D. E. J. Am. Chem. Soc. 1990, 112, 2814. (d) Heeres, H. J.; Heeres, A.; Teuben, J. H. Organometallics 1990, 9, 1508. (e) Hill, J. E.; Fanwick, P. E.; Rothwell, I. P. Organometallics, 1990, 9, 2211. (f) Smith, D. P.; Strickler, J. R.; Gray, S. D.; Bruck, M. A.; Holmes, R. S.; Wigley, D. E. Organometallics 1992, 11, 1275. (g) Hill, J. E.; Balaich, G.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1993, 12, 2911. (h) van der Linden, A.; Schaverien, C. J.; Meijboom, N.; Ganter, C.; Orpen, A. G. J. Am. Chem. Soc. 1995, 117, 3008. (i) Sigman, M. S.; Fatland, A. W.; Eaton, B. E. J. Am. Chem. Soc. 1998, 120, 5130.
15. See, for example: (a) Johnson, E. S.; Balaich, G. J.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 11086. (b) Bonanno, J. B.; Lobkovsky, E. B.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 11159. (c) Miller, R. L.; Toreki, R.; Lapointe, R. E.; Wolczanski, P. T.; Van Duyne, G.; Roe, D. C. J. Am. Chem. Soc. 1993, 115, 5570. (d) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 4, 656. (e) Arney, D. J.; Wexler, P. A.; Wigley, D. E. Organometallics 1990, 9, 1282. (f) Chisholm, M. H.; Rothwell, I. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Permagon: Oxford, 1988; Vol. 2, Chapter 15.3.
16. See, for example: (a) Johnson, E. S.; Balaich, G. J.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 11086. (b) Bonanno, J. B.; Lobkovsky, E. B.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 11159. (c) Miller, R. L.; Toreki, R.; Lapointe, R. E.; Wolczanski, P. T.; Van Duyne, G.; Roe, D. C. J. Am. Chem. Soc. 1993, 115, 5570. (d) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 4, 656. (e) Arney, D. J.; Wexler, P. A.; Wigley, D. E. Organometallics 1990, 9, 1282. (f) Chisholm, M. H.; Rothwell, I. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Permagon: Oxford, 1988; Vol. 2, Chapter 15.3.
17. See, for example: (a) Johnson, E. S.; Balaich, G. J.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 11086. (b) Bonanno, J. B.; Lobkovsky, E. B.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 11159. (c) Miller, R. L.; Toreki, R.; Lapointe, R. E.; Wolczanski, P. T.; Van Duyne, G.; Roe, D. C. J. Am. Chem. Soc. 1993, 115, 5570. (d) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 4, 656. (e) Arney, D. J.; Wexler, P. A.; Wigley, D. E. Organometallics 1990, 9, 1282. (f) Chisholm, M. H.; Rothwell, I. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Permagon: Oxford, 1988; Vol. 2, Chapter 15.3.
18. See, for example: (a) Johnson, E. S.; Balaich, G. J.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 11086. (b) Bonanno, J. B.; Lobkovsky, E. B.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 11159. (c) Miller, R. L.; Toreki, R.; Lapointe, R. E.; Wolczanski, P. T.; Van Duyne, G.; Roe, D. C. J. Am. Chem. Soc. 1993, 115, 5570. (d) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 4, 656. (e) Arney, D. J.; Wexler, P. A.; Wigley, D. E. Organometallics 1990, 9, 1282. (f) Chisholm, M. H.; Rothwell, I. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Permagon: Oxford, 1988; Vol. 2, Chapter 15.3.
19. See, for example: (a) Johnson, E. S.; Balaich, G. J.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 11086. (b) Bonanno, J. B.; Lobkovsky, E. B.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 11159. (c) Miller, R. L.; Toreki, R.; Lapointe, R. E.; Wolczanski, P. T.; Van Duyne, G.; Roe, D. C. J. Am. Chem. Soc. 1993, 115, 5570. (d) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 4, 656. (e) Arney, D. J.; Wexler, P. A.; Wigley, D. E. Organometallics 1990, 9, 1282. (f) Chisholm, M. H.; Rothwell, I. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Permagon: Oxford, 1988; Vol. 2, Chapter 15.3.
20. See, for example: (a) Johnson, E. S.; Balaich, G. J.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1997, 119, 11086. (b) Bonanno, J. B.; Lobkovsky, E. B.; Wolczanski, P. T. J. Am. Chem. Soc. 1994, 116, 11159. (c) Miller, R. L.; Toreki, R.; Lapointe, R. E.; Wolczanski, P. T.; Van Duyne, G.; Roe, D. C. J. Am. Chem. Soc. 1993, 115, 5570. (d) Balaich, G. J.; Hill, J. E.; Waratuke, S. A.; Fanwick, P. E.; Rothwell, I. P. Organometallics 1995, 14, 4, 656. (e) Arney, D. J.; Wexler, P. A.; Wigley, D. E. Organometallics 1990, 9, 1282. (f) Chisholm, M. H.; Rothwell, I. P. In Comprehensive Organometallic Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Permagon: Oxford, 1988; Vol. 2, Chapter 15.3.
21. See, for example: (a) Zanotti-Gerosa, A.; Solari, E.; Giannini, L.; Floriani, C.; Re, N.; Chiesi-Villa, A.; Rizzoli, C. Inorg. Chim. Acta. 1998, 270, 298. (b) Castellano, B.; Zanotti-Gerosa, A.; Solari, E.; Floriani, C. Organometallics 1996, 15, 4894. (c) Giannini, L.; Caselli, A.; Solari, E.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C.; Re, N.; Sgamellotti, A. J. Am. Chem. Soc. 1997, 119, 9709. (d) Olmstead, M. M.; Sigel, G.; Hope, H.; Xu, X.; Power, P. P. J. Am. Chem. Soc. 1985, 107, 8087.
22. See, for example: (a) Zanotti-Gerosa, A.; Solari, E.; Giannini, L.; Floriani, C.; Re, N.; Chiesi-Villa, A.; Rizzoli, C. Inorg. Chim. Acta. 1998, 270, 298. (b) Castellano, B.; Zanotti-Gerosa, A.; Solari, E.; Floriani, C. Organometallics 1996, 15, 4894. (c) Giannini, L.; Caselli, A.; Solari, E.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C.; Re, N.; Sgamellotti, A. J. Am. Chem. Soc. 1997, 119, 9709. (d) Olmstead, M. M.; Sigel, G.; Hope, H.; Xu, X.; Power, P. P. J. Am. Chem. Soc. 1985, 107, 8087.
23. See, for example: (a) Zanotti-Gerosa, A.; Solari, E.; Giannini, L.; Floriani, C.; Re, N.; Chiesi-Villa, A.; Rizzoli, C. Inorg. Chim. Acta. 1998, 270, 298. (b) Castellano, B.; Zanotti-Gerosa, A.; Solari, E.; Floriani, C. Organometallics 1996, 15, 4894. (c) Giannini, L.; Caselli, A.; Solari, E.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C.; Re, N.; Sgamellotti, A. J. Am. Chem. Soc. 1997, 119, 9709. (d) Olmstead, M. M.; Sigel, G.; Hope, H.; Xu, X.; Power, P. P. J. Am. Chem. Soc. 1985, 107, 8087.
24. See, for example: (a) Zanotti-Gerosa, A.; Solari, E.; Giannini, L.; Floriani, C.; Re, N.; Chiesi-Villa, A.; Rizzoli, C. Inorg. Chim. Acta. 1998, 270, 298. (b) Castellano, B.; Zanotti-Gerosa, A.; Solari, E.; Floriani, C. Organometallics 1996, 15, 4894. (c) Giannini, L.; Caselli, A.; Solari, E.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C.; Re, N.; Sgamellotti, A. J. Am. Chem. Soc. 1997, 119, 9709. (d) Olmstead, M. M.; Sigel, G.; Hope, H.; Xu, X.; Power, P. P. J. Am. Chem. Soc. 1985, 107, 8087.
25. Fan, M.; Zhang, H.; Lattman, M. Organometallics 1996, 15, 5216.
26. 3). Full characterization data are available as Supporting Information.
27. 3, R(F ≥ 4σ(F)) = 0.123, GOF = 1.19. Data for 1 were collected at 173 K on a Nonius Kappa CCD diffractometer. The calixarene moiety resides on an inversion center, although the moiety itself does not possess an inversion center. Thus, the structure was modeled with Sil and Til occupying the same position with 50% occupancies and equivalent thermal parameters. Two large peaks roughly 2.2 Å from Til were labeled as C11 and C12 and given 50% occupancies, which subsequently led to the discovery of two smaller peaks roughly 1.8 Å from Sil, which were labeled C23 and C24, respectively. Full structural details are available as Supporting Information.
28. Selected interatomic distances (Å): Til-C11 = 2.243(9), Til-C12 = 2.198(6), Til-O1 = 1.712(4), Til-O2 = 1.708(5). Selected bond angles (deg): C11-Til-C12 = 106.0(3), C11-Til-O1 = 110.4(3), C11-Til-O2 = 111.8(3), C12-Til-O1 = 110.7(2), C12-Til-O2 = 111.6(3), O1-Til -O2 = 106.4(2).
29. Gunther, H. NMR Spectroscopy: An Introduction; Wiley: New York, 1980; pp 77-86.
30. 2] (1) does not react with sodium metal even after 48 h.
31. 2 species with bridging diacetylide ligands, see: (a) Pulst, S.; Arndt, P.; Heller, B.; Baumann, W.; Kempe, R.; Rosenthal, U. Angew. Chem., Int. Ed. Engl. 1996, 35, 1112. (b) Pellny, P.-M.; Peulecke, N.; Burkalov, V. V.; Tillack, A.; Baumann, W.; Spannenberg, A.; Kempe, R.; Rosenthal, U. Angew. Chem., Int. Ed. Engl. 1997, 36, 2615. (c) Stucky, G. D.; Sekutowski, D. G. J. Am. Chem. Soc. 1976, 98, 1376.
32. 2 species with bridging diacetylide ligands, see: (a) Pulst, S.; Arndt, P.; Heller, B.; Baumann, W.; Kempe, R.; Rosenthal, U. Angew. Chem., Int. Ed. Engl. 1996, 35, 1112. (b) Pellny, P.-M.; Peulecke, N.; Burkalov, V. V.; Tillack, A.; Baumann, W.; Spannenberg, A.; Kempe, R.; Rosenthal, U. Angew. Chem., Int. Ed. Engl. 1997, 36, 2615. (c) Stucky, G. D.; Sekutowski, D. G. J. Am. Chem. Soc. 1976, 98, 1376.
33. 2 species with bridging diacetylide ligands, see: (a) Pulst, S.; Arndt, P.; Heller, B.; Baumann, W.; Kempe, R.; Rosenthal, U. Angew. Chem., Int. Ed. Engl. 1996, 35, 1112. (b) Pellny, P.-M.; Peulecke, N.; Burkalov, V. V.; Tillack, A.; Baumann, W.; Spannenberg, A.; Kempe, R.; Rosenthal, U. Angew. Chem., Int. Ed. Engl. 1997, 36, 2615. (c) Stucky, G. D.; Sekutowski, D. G. J. Am. Chem. Soc. 1976, 98, 1376.
34. Buchwald, S. L.; Nielsen, R. B. J. Am. Chem. Soc. 1989, 111, 2870.
35. Bruck, M. A.; Copenhaver, A. S.; Wigley, D. E. J. Am. Chem. Soc. 1987, 109, 6525.
36. Wielstra, Y.; Gambarotta, S.; Meetsma, A.; de Boer, J. L.; Chiang, M. Y. Organometallics 1989, 8, 2696.
37. Strickler, J. R.; Wexler, P. A.; Wigley, D. E. Organometallics 1988, 7, 2067.
38. 1H NMR data with that of an authentic sample.
39. 3), 0.04 (s, 3H, exo-SiMe), -1.48 (s, 3H, endo-SiMe). In addition, protonolysis of 2a with MeOH produced trimethylsilylacetylene in near-quantitative yield.
40. Decomposition of 2a yields a complex mixture of products. Nonetheless, 1,4-bis(trimethylsilyl)butadiyne could be readily identified.
41. 3Ti (2b): C, 72.30; H, 7.85; N, 2.48. Found: C, 72.04; H, 8.21; N, 2.42. Full characterization data are available as Supporting Information.
42. The slight decrease in regioselectivity is due presumably to a change in the stereochemical environment about titanium (from tetrahedral geometry) as a result of the coordination of a THF molecule.
43. Durfee, L. D.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1987, 109, 4720.