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Superelectrophilic amidine dications: dealkylation by triflate anion.

Angewandte Chemie (International ed. in English) (2012-07-19)
Luka S Kovacevic, Christopher Idziak, Augustinas Markevicius, Callum Scullion, Michael J Corr, Alan R Kennedy, Tell Tuttle, John A Murphy
ABSTRACT

Superelectrophiles: Formamides were designed that when treated with triflic anhydride would be transformed into superelectrophilic amidine dications. These dications were so electrophilic that they underwent in situ dealkylation by the triflate anion (see scheme; Tf = trifluoromethanesulfonyl). DFT calculations were used to determine the mechanistic details of the dealkylation reaction.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Trifluoromethanesulfonic acid, ReagentPlus®, ≥99%
Sigma-Aldrich
Lithium trifluoromethanesulfonate, 99.995% trace metals basis
Sigma-Aldrich
Lithium trifluoromethanesulfonate, 96%
Sigma-Aldrich
Lanthanum(III) trifluoromethanesulfonate, 99.999% trace metals basis
Sigma-Aldrich
Zinc trifluoromethanesulfonate, 98%
Sigma-Aldrich
Trifluoromethanesulfonic acid, reagent grade, 98%
Sigma-Aldrich
Silver trifluoromethanesulfonate, ≥99%
Sigma-Aldrich
Aluminum trifluoromethanesulfonate, 99.9% trace metals basis
Sigma-Aldrich
Silver trifluoromethanesulfonate, ≥99.95% trace metals basis
Sigma-Aldrich
Silver trifluoromethanesulfonate, purum, ≥98.0% (Ag)