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Quantification of the electrophilicities of dithiocarbenium ions

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Abstract

The reactions of the dithio substituted carbenium ions 2a-c with allylsilanes, allylstannanes (3), and silylated enol ethers (4) which yield dithioacetal protected β, ψ-unsaturated carbonyl compounds (7) and selectively protected 1,3-dicarbonyl compounds (8), have been studied kinetically. The second-order rate constants have been used to determine the electrophilicity parameters for the [1,3]dithiolan-2-ylium ion 2a (E=−6.25) and the [1,3]dithian-2-ylium ions 2b (E=−6.82) and 2c (E=−2.17). It is shown how these parameters can be used to predict the electrophilic potential of 2a-c.

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Authors and Affiliations

  1. Institut für Organische Chemie der Technischen Hochschule Darmstadt, Petersenstraße 22, D-64287, Darmstadt, Germany

    H. Mayr, J. Henninger & T. Siegmund

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  1. H. Mayr
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  2. J. Henninger
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  3. T. Siegmund
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Dedicated to Prof. George A. Olah who imbued carbocations with immortality.

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Mayr, H., Henninger, J. & Siegmund, T. Quantification of the electrophilicities of dithiocarbenium ions. Res. Chem. Intermed. 22, 821–838 (1996). https://doi.org/10.1163/156856796X00502

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  • DOI: https://doi.org/10.1163/156856796X00502

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