Next Article in Journal
Synthesis and Evaluation of New 1,3,4-Thiadiazole Derivatives as Antinociceptive Agents
Next Article in Special Issue
σ-Bond Electron Delocalization in Oligosilanes as Function of Substitution Pattern, Chain Length, and Spatial Orientation
Previous Article in Journal
The in Vitro and in Vivo Antitumor Activities of Tetracyclic Triterpenoids Compounds Actein and 26-Deoxyactein Isolated from Rhizome of Cimicifuga foetida L.
Previous Article in Special Issue
Isolation of a Cyclic (Alkyl)(amino)germylene
Article Menu
Issue 8 (August) cover image

Export Article

Open AccessArticle
Molecules 2016, 21(8), 999; doi:10.3390/molecules21080999

Intramolecular Chain Hydrosilylation of Alkynylphenylsilanes Using a Silyl Cation as a Chain Carrier

1
Faculty of Education, University of Miyazaki, 1-1 Gakuen Kibanadai Nishi, Miyazaki, 889-2192 Miyazaki, Japan
2
Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, 171-8588 Tokyo, Japan
3
Graduate School of Science and Technology, Gunma University, 1-5-1 Tenjin-cho, Kiryu, 376-8515 Gunma, Japan
*
Authors to whom correspondence should be addressed.
Academic Editor: Mitsuo Kira
Received: 9 July 2016 / Revised: 25 July 2016 / Accepted: 27 July 2016 / Published: 1 August 2016
(This article belongs to the Special Issue Advances in Silicon Chemistry)
View Full-Text   |   Download PDF [921 KB, uploaded 1 August 2016]   |  

Abstract

Diorganyl[2-(trimethylsilylethynyl)phenyl]silanes 1ac and methyl-substituted phenylsilanes 1d and 1e were treated with a small amount of trityl tetrakis(pentafluorophenyl)borate (TPFPB) as an initiator in benzene to afford the corresponding benzosiloles (2ae) in moderate to good yields. However, no reaction was observed for the reaction using [2-(1-hexynyl)phenyl]diisopropylsilane lf. The methyl substituent was tolerated under the reaction conditions and increased the yield of the corresponding benzosilole depending on the substitution position. From the result using 1f, the current reaction was found to require the trimethylsilyl group, which can stabilize intermediary alkenyl carbocations by the β-silyl effect. The current reaction can be considered an intramolecular chain hydrosilylation of alkynylarylsilanes involving silyl cations as chain carriers. Therefore, the silyl cations generated by hydride abstraction from hydrosilanes 1 with the trityl cation causes intramolecular electrophilic addition to the C-C triple bond to form ethenyl cations, which abstract a hydride from 1 to afford benzosiloles 2 with the regeneration of the silyl cations. View Full-Text
Keywords: benzosilole; silyl cation; hydrosilylation; metal free benzosilole; silyl cation; hydrosilylation; metal free
Figures

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Supplementary material

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Arii, H.; Nakabayashi, K.; Mochida, K.; Kawashima, T. Intramolecular Chain Hydrosilylation of Alkynylphenylsilanes Using a Silyl Cation as a Chain Carrier. Molecules 2016, 21, 999.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]

Molecules EISSN 1420-3049 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top