Inherent oxygen preference in enolate monofluoromethylation and a synthetic entry to monofluoromethyl ethers

Article abstract of DOI:10.1002/anie.201006218

Expect the unexpected: The self-stable salts 1, X=OTf, PF₆, x=2, y=1, developed for electrophilic monofluoromethylation showed inherent selectivity for the O-alkylation of enolates, thus providing access to monofluoromethyl ethers, which are difficult to obtain by the direct electrophilic fluoromethylation of alcohols. Salt 1, X=BF₄, x=0, y=3, in contrast leads to C-alkylated products.