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.
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.
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.
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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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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DOI: https://doi.org/10.1007/128_2015_658
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