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Long‐Lived Trifluoromethanide Anion: A Key Intermediate in Nucleophilic Trifluoromethylations
Author(s) -
Prakash G. K. Surya,
Wang Fang,
Zhang Zhe,
Haiges Ralf,
Rahm Martin,
Christe Karl O.,
Mathew Thomas,
Olah George A.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201406505
Subject(s) - trifluoromethylation , nucleophile , electrophile , chemistry , ion , nuclear magnetic resonance spectroscopy , nucleophilic addition , spectroscopy , photochemistry , computational chemistry , medicinal chemistry , organic chemistry , catalysis , physics , trifluoromethyl , alkyl , quantum mechanics
Abstract The trifluoromethanide anion is the postulated key intermediate in nucleophilic trifluoromethylation reactions. However, for more than six decades, the trifluoromethanide anion was widely believed to exist only as a short‐lived transient species in the condensed phase. It has now been prepared in bulk for the first time in THF solution. The trifluoromethanide anion with the [K(18‐crown‐6)] + cation was unequivocally characterized by low‐temperature 19 F and 13 C NMR spectroscopy. Its intermediacy in nucleophilic trifluoromethylation reactions was directly evident by its reaction chemistry with various electrophilic substrates. Variable‐temperature NMR spectroscopy, along with quantum mechanical calculations, support the persistence of the trifluoromethanide anion.