Synthetic applications of the carbanion generated from 4,4,4-trifluorobutan-2-one

Formation of Quaternary Carbon Center with a Trifluoromethyl Group Using a Pd-Catalyzed Allylation Reaction

“…Tetramethylsilane (TMS) was used as an internal standard. 19 F-NMR spectra were recorded on Hitachi FT-NMR R-1500 and JEOL-ECA-600SN spectrometers. Benzotrifluoride (BTF) was used as an internal standard.…”

“…19,20) Furthermore, recently, Ishihara and his co-workers reported a Pd-catalyzed allylation of trifluoroalanine derivatives. 21) They obtained the products which was forming a carbon-carbon bond at the active methylene carbon in moderate to good yields.…”

The synthesis of fluorinated materials in microreactors

“…While we have reported the synthesis and synthetic application of silylenol ether of 4,4,4-trifluorobutan-2-one [6] at À78 8C in a flask, several problems remain unsolved in the field of b-fluorocarbanions. In particular, compound 5 (entries 1 and 2: Ph (26%), 4-MeOC 6 H 4 (45%)) via the silylenol ether 3 was obtained as a minor material in the reaction at room temperature, however, compound 5 was not produced at À78 8C and in microreactor.…”

Construction of Trifluoromethyl‐Bearing Quaternary Carbon Centers by Intramolecular Decarboxylative Allylation of α‐Trifluoromethyl β‐Keto Esters

“…[8] Despite its potential usefulness in synthetic chemistry, Kitazumes methodology has been given scant attention and only a few reports of related palladium-catalyzed intermolecular allylation reactions have appeared, essentially due to the limitations in substrate preparation. [9,10] We recently developed efficient methods to prepare a broad range of a-trifluoromethyl-b-keto esters containing diverse functionality by direct trifluoromethylation of b-keto esters using either CF 3 I, [11] or electrophilic trifluoromethylation reagents [12] in high yields. Taking advantage from a practical preparation of the a-trifluoromethyl-b-keto esters, [11][12][13] we thought the intramolecular version of Kitazumes approach could provide a unique means for constructing trifluoromethylated products.…”

“…These compounds are attractive building blocks for medicinal chemistry and also interesting from a synthetic point of view, because these cyclic compounds are difficult to obtain by intermolecular allylation reactions. [8][9][10] …”