Thermodynamic: Versus kinetic control in substituent redistribution reactions of silylium ions steered by the counteranion

Cited 0 time in webofscience Cited 0 time in scopus
38 Viewed 13 Downloaded
Title
Thermodynamic: Versus kinetic control in substituent redistribution reactions of silylium ions steered by the counteranion
Author(s)
Lukas Omann; Bimal Pudasaini; Elisabeth Irran; a Hendrik F. T. Klare; Mu-Hyun Baik; Martin Oestreich
Publication Date
2018-07
Journal
CHEMICAL SCIENCE, v.9, no.25, pp.5600 - 5607
Publisher
ROYAL SOC CHEMISTRY
Abstract
An in-depth experimental and theoretical study of the substituent exchange reaction of silylium ions is presented. Apart from the substitution pattern at the silicon atom, the selectivity of this process is predominantly influenced by the counteranion, which is introduced with the trityl salt in the silylium ion generation. In contrast to Müller's protocol for the synthesis of triarylsilylium ions under kinetic control, the use of Reed's carborane anions leads to contact ion pairs, allowing selective formation of trialkylsilylium ions under thermodynamic control. DFT calculations finally revealed an unexpected mechanism for the rate-determining alkyl exchange step, which is initiated by an unusual 1,2-silyl migration in the intermediate ipso-disilylated arenium ion. The resulting ortho-disilylated arenium ion can then undergo an alkyl transfer via a low-barrier five-centered transition state. © 2018 The Royal Society of Chemistry
URI
https://pr.ibs.re.kr/handle/8788114/4950
ISSN
2041-6520
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
Files in This Item:
baik_Thermodynamic versus kinetic control in.pdfDownload

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse