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Synthesis 2023; 55(10): 1602-1612
DOI: 10.1055/a-2009-8114
DOI: 10.1055/a-2009-8114
paper
Silylium Ion Initiated Intramolecular Friedel–Crafts-Type Cyclization of 1,1-Difluoroalkenes with Subsequent Hydrodefluorination of C(sp3)–F Bonds
A.R. and H.G. thank the Berlin Graduate School of Natural Sciences and Engineering for predoctoral fellowships (2018–2021 and 2020–2023, respectively). Generous funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy (EXC 2008/1 – 390540038, UniSysCat) is gratefully acknowledged. M.O. is indebted to the Einstein Foundation Berlin for an endowed professorship.
Abstract
The strong electrophilicity of silylium ions has been leveraged to probe an intramolecular Friedel–Crafts-type cyclization of aryl-tethered 1,1-difluoroalkenes. The reaction is presumed to be initiated by a preferential electrophilic silylation of the carbon–carbon double bond over the activation of one of the vinylic C(sp2)–F bonds. Subsequent cyclization followed by hydrodefluorination of the resulting C(sp3)–F bonds leads to the final product. The resulting tetraline derivatives were obtained in moderate to good yields. Distinct from earlier reports, the reaction proceeds with the perfluorinated tetraphenylborate counteranion under ambient conditions without the prerequisite of a carborate counteranion associated with the silylium ion intermediates.
Key words
carbenium ions - cyclization - Friedel–Crafts reaction - hydrodefluorination - Lewis acids - silicon - silylium ionsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2009-8114.
- Supporting Information
Publication History
Received: 21 December 2022
Accepted after revision: 09 January 2023
Accepted Manuscript online:
09 January 2023
Article published online:
08 February 2023
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For a recent review on transition-metal-free C–F bond activation, see:
Selected treatises on fluorinated carbocations:
For a quantum chemical prediction, see: