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Journals / Turkish Journal of Chemistry / 2010 / Cilt: 34 - Sayı: 5

Effect of various substituents on intramolecular 1,1-vinylboration, synthesis of 1-silacyclobutene derivatives

Ezzat KHAN
Bernd WRACKMEYER
Pages
793–803
Publication Date
2010-05-01
DOI
—
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AI Summary & Key Takeaways

AI Insight
⚡ TL;DR(Too Long; Didn't Read)

The reactions were monitored by NMR spectroscopy in order to elucidate the reaction mechanism, and the proposed structures of all new compounds follow from consistent sets of NMR parameters (1H-, 13C-, 11B-, 29Si-NMR).

📌 3 Key Takeaways

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Objective & Hypothesis:The reaction of 1-boryl-1-alkenyl chlorosilane derivatives with alkynyllithium reagents [Li-C\equiv C-R3 (R3~=~Ph, SiMe3)] at low temperature (--78 °C) affords alkenyl(alkyn-1-yl)silanes.
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Key Findings & Data:These compounds are precursors of 1-silacyclobutene derivatives, which are formed via intramolecular 1,1-vinylboration.
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Conclusion & Impact:The reactions were monitored by NMR spectroscopy in order to elucidate the reaction mechanism, and the proposed structures of all new compounds follow from consistent sets of NMR parameters (1H-, 13C-, 11B-, 29Si-NMR).
🔬Design:Research Article
📍Scope:Comprehensive Sample
⚙️Variables:Alkynylsilanes · triorganoboranes · hydroboration

Abstract

The reaction of 1-boryl-1-alkenyl chlorosilane derivatives with alkynyllithium reagents [Li-C\equiv C-R3 (R3~=~Ph, SiMe3)] at low temperature (--78 °C) affords alkenyl(alkyn-1-yl)silanes. These compounds are precursors of 1-silacyclobutene derivatives, which are formed via intramolecular 1,1-vinylboration. This reaction works for various groups at silicon (R1/R2: R1 = H, Me, Ph; R2 = Me, Ph) and at the C=C and C\equiv C units (R/R3: R = nBu, Ph; R3 = nBu, Ph, SiMe3). The conversion into 1-silacyclobutene derivatives is incomplete only in the case of R3 = SiMe3. The reactions were monitored by NMR spectroscopy in order to elucidate the reaction mechanism, and the proposed structures of all new compounds follow from consistent sets of NMR parameters (1H-, 13C-, 11B-, 29Si-NMR).

Özet

The reaction of 1-boryl-1-alkenyl chlorosilane derivatives with alkynyllithium reagents [Li-C\equiv C-R3 (R3~=~Ph, SiMe3)] at low temperature (--78 °C) affords alkenyl(alkyn-1-yl)silanes. These compounds are precursors of 1-silacyclobutene derivatives, which are formed via intramolecular 1,1-vinylboration. This reaction works for various groups at silicon (R1/R2: R1 = H, Me, Ph; R2 = Me, Ph) and at the C=C and C\equiv C units (R/R3: R = nBu, Ph; R3 = nBu, Ph, SiMe3). The conversion into 1-silacyclobutene derivatives is incomplete only in the case of R3 = SiMe3. The reactions were monitored by NMR spectroscopy in order to elucidate the reaction mechanism, and the proposed structures of all new compounds follow from consistent sets of NMR parameters (1H-, 13C-, 11B-, 29Si-NMR).

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Cite This Article

KHAN, E., WRACKMEYER, B. (2010). Effect of various substituents on intramolecular 1,1-vinylboration, synthesis of 1-silacyclobutene derivatives. Turkish Journal of Chemistry, Cilt: 34 - Sayı: 5, 793–803. https://ajindex.com/articles/185128

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References (25)

  1. Brown, H. C. Organic Synthesis via Boranes, Wiley Interscience, New York, 1975.
  2. Burke, L. P.; Negishi, E.; Brown, H. C. J. Am. Chem. Soc. 1973, 95, 3654-3562.
  3. Mulzer, J.; Altenbach, H.-J.; Braun, M.; Krohn, K.; Reissig, H.-U. (Eds.) Organic Synthesis Highlights; Wiley Interscience, New York, 1991, pp. 33. Hall, D. G. (Eds.), Boronic Acids, Preparation, Applications in Organic Synthesis and Medicine, Wiley Interscience, New York, 2005.
  4. Wrackmeyer, B. Coord. Chem. Rev. 1995, 145, 125-156.
  5. Wrackmeyer, B. Heteroatom Chem. 2006, 17, 188-206.
  6. Wrackmeyer, B.; Tok, O. L. Comprehensive Heterocyclic Chemistry III; Eds.: Katritzky, A. R.; Ramsden, C. A.; Scriven, E. F. V.; Taylor, R. J. K.; Elsevier, Oxford, 2008, pp. 1181-1223.
  7. Soderquist, J. A.; Colberg, J. C.; DelValle, L. J. Am. Chem. Soc. 1989, 111, 4873-4878.
  8. Soderquist, J. A.; Leon, G. Tetrahedron Lett. 1998, 39, 3989-3990.
  9. Uchida, K.; Utimoto, K.; Nozaki, H. J. Org. Chem. 1976, 41, 2941-2942.
  10. Uchida, K.; Utimoto, K.; Nozaki, H. Tetrahedron 1977, 33, 2987-2992.
  11. Rajogopalan, S.; Zweifel, G. Synthesis 1984, 113-115.
  12. Miller, J. A.; Zweifel, G. Synthesis 1981, 288. Miller, J. A.; Zweifel, G. J. Am. Chem. Soc. 1981, 103, 6217-6219.
  13. Zweifel, G.; Backlund, S. J. J. Am. Chem. Soc. 1977, 99, 3184-3185.
  14. Wrackmeyer, B.; Maisel, H. E.; Milius, W.; Bhatti, M. H.; Ali, S. J. Organomet. Chem. 2003, 669, 72-78. K¨oster, R.; Seidel, G.; S¨uß, J.; Wrackmeyer, B. Chem. Ber. 1993, 126, 1107-1114.
  15. Wrackmeyer, B.; Kehr, G.; S¨uß, J. Chem. Ber. 1993, 126, 2221-2226.
  16. Wrackmeyer, B.; Maisel, H. E.; S¨uß, J.; Milius, W. Z. Naturforsch. 1996, 51b, 1320-1324.
  17. Wrackmeyer, B.; Kehr, G.; S¨uß, J.; Molla, E. J. Organomrt. Chem. 1998, 562, 207-215.
  18. Wrackmeyer, B.; S¨uß, J. Z. Naturforsch. 2002, 57b, 741-745.
  19. Wrackmeyer, B.; Khan, E.; Kempe, R. Z. Anorg. Allg. Chem. 2007, 633, 453-457. K¨oster, R.; Sch¨ußler, W.; Boese, R.; Herberhold, M.; Gerstmann, S.; Wrackmeyer, B. Chem, Ber, 1996, 129, 507. Wrackmeyer, B.; Tok, O. L.; Bubnov, Y. N. Angew Chem. Int. Ed. 1999, 38, 124-126.
  20. Wrackmeyer, B.; Schanz, H.-J.; Hofmann, M.; Schleyer, P. v. R.; Boese, R. Eur. J. Inorg. Chem. 1999, 533-537.
  21. Wrackmeyer, B.; Badshah, A.; Molla, E.; Motalib, A. J. Organomet. Chem. 1999, 584, 98-102.
  22. Wrackmeyer, B.; Bhatti, M. H.; Ali, S.; Tok, O. L.; Bubnov, Y. N. J. Organomet. Chem. 2002, 657, 146-154.
  23. Wrackmeyer, B.; Shahid, K.; Ali, S. Appl. Organomet. Chem. 2005, 19, 377-382.
  24. Wrackmeyer, B.; Shahid, K.; Ali, S. Z. Naturforsch. 2005, 60b, 590-592.
  25. Wrackmeyer, B.; M