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Hypervalent Iodine Chemistry pp 167–186Cite as

Iodanes as Trifluoromethylation Reagents

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Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 373))

Abstract

This chapter describes synthesis, structural properties, activation modes, and applications of hypervalent iodine reagents for trifluoromethylation, thereby focusing on recent advances.

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Notes

  1. 1.

    Inverse kinetic isotope effects are often observed for reactions with a rapid pre-equilibrium for protonation/deprotonation because of the deuterated intermediate being a weaker acid and thus accumulating larger concentrations of the steady-state intermediate before the rate-determining step.

  2. 2.

    The recent literature about trifluoromethylation reactions with compounds 1 and 2 often conveys “hypothetical” or “postulated” mechanistic schemes not backed up by experiments. While such mechanistic suggestions may be realistic, they still need to be examined in a very critical manner.

  3. 3.

    It is often assumed that the formation of a TEMPO-CF3 adduct demonstrates a radical pathway. However, it is often not clear whether the radical pathway is actually part of the trifluoromethylation reaction of the substrate or whether it is actually induced by the presence of TEMPO, because TEMPO is a trifluoromethylation substrate itself in the absence of a stronger nucleophile, under a series of conditions.

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Authors and Affiliations

  1. Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, Vladimir-Prelog-Weg 2, 8093, Zürich, Switzerland

    Natalja Früh, Julie Charpentier & Antonio Togni

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  1. Natalja Früh
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  2. Julie Charpentier
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  3. Antonio Togni
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Correspondence to Antonio Togni .

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  1. School of Chemistry, Cardiff University , Cardiff, United Kingdom

    Thomas Wirth

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Früh, N., Charpentier, J., Togni, A. (2015). Iodanes as Trifluoromethylation Reagents. In: Wirth, T. (eds) Hypervalent Iodine Chemistry. Topics in Current Chemistry, vol 373. Springer, Cham. https://doi.org/10.1007/128_2015_658

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