2324-98-3Relevant articles and documents
The fragmentation of polyfluorinated benzylic alcohols: the first observation of pentafluorophenyl anion as a good leaving group
Garner, Charles M.,Fisher, Henry C.
, p. 7405 - 7407 (2006)
Treatment of a series of pentafluorobenzylic alcohols with sodium methoxide in DMSO results in a rapid carbon-carbon cleavage reaction, yielding a ketone or aldehyde as well as pentafluorobenzene, which undergoes subsequent nucleophilic aromatic substitution (NAS). In methanol solvent, the fragmentation is very slow, and NAS without fragmentation occurs almost exclusively. In methanol/DMSO mixtures, both processes are observed simultaneously. This appears to be the first report of the fragmentation of pentafluorobenzylic alcohols.
Transition-Metal-Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate
Kikushima, Kotaro,Grellier, Mary,Ohashi, Masato,Ogoshi, Sensuke
supporting information, p. 16191 - 16196 (2017/11/27)
A transition-metal-free catalytic hydrodefluorination (HDF) reaction of polyfluoroarenes is described. The reaction involves direct hydride transfer from a hydrosilicate as the key intermediate, which is generated from a hydrosilane and a fluoride salt. The eliminated fluoride regenerates the hydrosilicate to complete the catalytic cycle. Dispersion-corrected DFT calculations indicated that the HDF reaction proceeds through a concerted nucleophilic aromatic substitution (CSNAr) process.
Synthesis of K[4-ROC6F4BF3] from potassium pentafluorophenyltrifluoroborate and O-nucleophiles
Shabalin, Anton Yu.,Adonin, Nicolay Yu.,Bardin, Vadim V.,Prikhod'Ko, Sergey A.,Timofeeva, Maria N.,Bykova, Maria V.,Parmon, Valentin N.
, p. 82 - 87 (2013/05/22)
A new route to potassium polyfluoroaryltrifluoroborates, K[4-ROC 6F4BF3], consisting in the nucleophilic alkoxydefluorination of K[C6F5BF3] with MOR (M = K, Na) in a polar aprotic solvent is suggested. Reaction of K[C 6F5BF3] with KO-t-Bu proceeds smoothly at 25 °C in DME, but the attempted alkoxydefluorination of K[C6F 5BF3] with other NaOR at 30 °C in DME failed. A series of K[4-ROC6F4BF3] (R = Me, Et, Pr, i-Pr, Bu, PhCH2) is prepared using the corresponding sodium alkoxides in DMF at 130 °C in 80-90% isolated yield. Salt K[4-CH2CHCH 2OC6F4BF3] is prepared at 100 °C whereas at 130 °C formation of 2,3,5,6-C6F4HOCH 2CHCH2 occurs. Salt K[4-PhOC6F 4BF3] is obtained in 82% yield using KOPh (2 equivalents) in DMSO at 130 °C.