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Keywords = β-silyl carbocations

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9 pages, 3118 KiB  
Article
Esterifications with 2-(Trimethylsilyl)ethyl 2,2,2-Trichloroacetimidate
by Wenhong Lin, Shea T. Meyer, Shawn Dormann and John D. Chisholm
Organics 2021, 2(1), 17-25; https://doi.org/10.3390/org2010002 - 4 Feb 2021
Cited by 1 | Viewed by 5900
Abstract
2-(Trimethylsilyl)ethyl 2,2,2-trichloroacetimidate is readily synthesized from 2-trimethylsilylethanol in high yield. This imidate is an effective reagent for the formation of 2-trimethylsilylethyl esters without the need for an exogenous promoter or catalyst, as the carboxylic acid substrate is acidic enough to promote ester formation [...] Read more.
2-(Trimethylsilyl)ethyl 2,2,2-trichloroacetimidate is readily synthesized from 2-trimethylsilylethanol in high yield. This imidate is an effective reagent for the formation of 2-trimethylsilylethyl esters without the need for an exogenous promoter or catalyst, as the carboxylic acid substrate is acidic enough to promote ester formation without an additive. A deuterium labeling study indicated that a β-silyl carbocation intermediate is involved in the transformation. Full article
(This article belongs to the Special Issue Feature Papers in Organics)
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7 pages, 921 KiB  
Article
Intramolecular Chain Hydrosilylation of Alkynylphenylsilanes Using a Silyl Cation as a Chain Carrier
by Hidekazu Arii, Kenichi Nakabayashi, Kunio Mochida and Takayuki Kawashima
Molecules 2016, 21(8), 999; https://doi.org/10.3390/molecules21080999 - 1 Aug 2016
Cited by 28 | Viewed by 5650
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Advances in Silicon Chemistry)
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