The influence of the organolithium reagent nature on the possibility of the O→Csp migration of the R3Si group in propynes HC≡CCH2OSiR3
- Authors: Novokshonov V.V.1, Medvedeva A.S.1, Mareev A.V.1
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Affiliations:
- A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
- Issue: Vol 66, No 12 (2017)
- Pages: 2264-2268
- Section: Full Article
- URL: https://journals.rcsi.science/1066-5285/article/view/241765
- DOI: https://doi.org/10.1007/s11172-017-2012-4
- ID: 241765
Cite item
Abstract
A possibility of the O→Csp 1,4-migration of the R3Si group in silyl ethers of terminal acetylenic alcohols upon treatment with organolithium reagents (RLi) was studied. In the case of 3-trimethylsilyloxypropyne, depending on the nature of RLi, the heterolysis of the Si—O bond occurs either by the action of acetylide formed as a result of deprotonation with the formation of 3-trimethylsilylprop-2-yn-1-ol trimethylsilyl ether, or by the action of the metalation agent with the formation of propargyl alcohol. The realization of the O→Csp 1,4-migration of the Me3Si group requires the use of mild organolithium reagents (lithium hexamethyldisilazanide and diisopropylamide). Silyl ethers having steric hindrance at the carbon atom bonded to the reaction center or around the silicon atom do not react with the studied organolithium reagents.
About the authors
V. V. Novokshonov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
Author for correspondence.
Email: vnov1971@gmail.com
Russian Federation, 1 ul. Favorskogo, Irkutsk, 664033
A. S. Medvedeva
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: vnov1971@gmail.com
Russian Federation, 1 ul. Favorskogo, Irkutsk, 664033
A. V. Mareev
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences
Email: vnov1971@gmail.com
Russian Federation, 1 ul. Favorskogo, Irkutsk, 664033