Different modes of reaction of monoalkoxy- and dialkoxyphenylchlorosilanes with lithium metal: Selective formation of (2-alkoxydisilanyl)lithium vs (dialkoxysilyl)lithium

Organometallics

Volumn 15, Issue 21, 1996, Pages 4653-4656

  Kawachi, Atsushi ^a   Tamao, Kohei ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0006546049     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960421i     Document Type: Article

References (26)

1. Review: (a) Tamao, K.; Kawachi, A. Adv. Organomet. Chem. 1995, 38, 1-58.
2. (a) Tamao, K.; Kawachi, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 818.
3. (b) Tamao, K.; Kawachi, A. Organometallics 1995, 14, 3108.
4. (c) Tamao, K.; Kawachi, A.; Ito, Y. J. Am. Chem. Soc. 1992, 114, 3989 and references cited therein.
5. Recent examples: (a) Ruehl, K. E.; Davis, M. E.; Matyjaszewski, K. Organometallics 1992, 11, 788. (b) Wakahara, T.; Akasaka, T.; Ando, W. Organometallics 1994, 13, 4683. (c) Belzner, J.; Dehnert, U.; Stalke, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 2450. (d) Sekiguchi, A.; Nanjo, M.; Kabuto, C.; Sakurai, H. Organometallics 1995, 14, 2630.
6. Recent examples: (a) Ruehl, K. E.; Davis, M. E.; Matyjaszewski, K. Organometallics 1992, 11, 788. (b) Wakahara, T.; Akasaka, T.; Ando, W. Organometallics 1994, 13, 4683. (c) Belzner, J.; Dehnert, U.; Stalke, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 2450. (d) Sekiguchi, A.; Nanjo, M.; Kabuto, C.; Sakurai, H. Organometallics 1995, 14, 2630.
7. Recent examples: (a) Ruehl, K. E.; Davis, M. E.; Matyjaszewski, K. Organometallics 1992, 11, 788. (b) Wakahara, T.; Akasaka, T.; Ando, W. Organometallics 1994, 13, 4683. (c) Belzner, J.; Dehnert, U.; Stalke, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 2450. (d) Sekiguchi, A.; Nanjo, M.; Kabuto, C.; Sakurai, H. Organometallics 1995, 14, 2630.
8. Recent examples: (a) Ruehl, K. E.; Davis, M. E.; Matyjaszewski, K. Organometallics 1992, 11, 788. (b) Wakahara, T.; Akasaka, T.; Ando, W. Organometallics 1994, 13, 4683. (c) Belzner, J.; Dehnert, U.; Stalke, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 2450. (d) Sekiguchi, A.; Nanjo, M.; Kabuto, C.; Sakurai, H. Organometallics 1995, 14, 2630.
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13. (e) Hiyama, T.; Obayashi, M.; Mori, I.; Nozaki, H. J. Org. Chem. 1983, 48, 912.
14. West, R. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, England, 1989; Chapter 19, and references cited therein.
15. For previous work on transient alkoxysilyl anions: (a) Watanabe, H.; Higuchi, K.; Kobayashi, M.; Hara, M.; Koike, Y.; Kitahara, T.; Nagai, Y. J. Chem. Soc., Chem. Commun. 1977, 534. (b) Watanabe, H.; Higuchi, K.; Goto, T.; Muraoka, T.; Inose, J.; Kageyama, M.; Iizuka, Y.; Nozaki, M.; Nagai, Y. J. Organomet. Chem. 1981, 218, 27.
16. For previous work on transient alkoxysilyl anions: (a) Watanabe, H.; Higuchi, K.; Kobayashi, M.; Hara, M.; Koike, Y.; Kitahara, T.; Nagai, Y. J. Chem. Soc., Chem. Commun. 1977, 534. (b) Watanabe, H.; Higuchi, K.; Goto, T.; Muraoka, T.; Inose, J.; Kageyama, M.; Iizuka, Y.; Nozaki, M.; Nagai, Y. J. Organomet. Chem. 1981, 218, 27.
17. Lithium dispersion gave 4 and 10 in much lower yields, together with uncharacterizable byproducts.
18. When only an equimolar amount of lithium metal was used at room temperature, 5 was obtained selectively in 60% yield (see Experimental Section).
19. In all cases, the chlorosilanes were consumed completely and uncharacterizable nonvolatile compounds were also obtained.
20. 2b in 25% yield and 1,3-di-tert-butoxy-1,1,2,2,3,3-hexaphenyltrisilane in 26% yield (see Experimental Section). The latter may be formed by reaction of 9a with 8a. The isolated disilane 11a, however, did not react with lithium (8 equiv) even under sonication at room temperature (100% recovery of 11a).
21. 2) by a similar elimination process has been reported so far: (a) Raabe, G.; Michl, J. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, England, 1989; Chapter 17, section III. (b) Okazaki, R.; West, R. Adv. Organomet. Chem. 1996, 39, 231-273.
22. 2) by a similar elimination process has been reported so far: (a) Raabe, G.; Michl, J. In The Chemistry of Organic Silicon Compounds; Patai, S., Rappoport, Z., Eds.; Wiley: Chichester, England, 1989; Chapter 17, section III. (b) Okazaki, R.; West, R. Adv. Organomet. Chem. 1996, 39, 231-273.
23. Weidenbruch, M.; Kramer, K.; Schäfer, A.; Blum, J. K. Chem. Ber. 1985, 118, 107.
24. (a) Tsumuraya, T.; Batcheller, S. A.; Masamune, S. Angew. Chem., Int. Ed. Engl. 1991, 30, 902 and references cited therein.
25. (b) Miller, R. D.; Michl, J. Chem. Rev. 1989, 89, 1359.
26. (c) Worsfold, D. J. In Inorganic and Organometallic Polymers; ACS Symposium Series 360; Zelden, M., Wynne, K. J., Allcock, H. R., Eds.; American Chemical Society: Washington, DC, 1988; Chapter 8, and references cited therein.