83168-79-0Relevant academic research and scientific papers
Palladium-Catalyzed Cross-Coupling Reaction of Alkyltrifluorosilanes with Aryl Halides
Matsuhashi, Hayao,Asai, Satoshi,Hirabayashi, Kazunori,Hatanaka, Yasuo,Mori, Atsunori,Hiyama, Tamejiro
, p. 437 - 444 (2007/10/03)
A cross-coupling reaction of alkyltrifluorosilanes with aryl halides was achieved using a catalytic amount of tetrakis-(triphenylphosphine)palladium(0) and excess of tetrabutylammonium fluoride (TBAF) at 100°C with high chemoselectitvity. Functional groups like nitro, ketone carbonyl, and formyl tolerated the coupling conditions. Because potassium(18-crown-6) alkyltetrafluorosilicates also underwent a cross-coupling reaction in the presence of an additional molar amount of TBAF, the active species of the coupling reaction was assumed to be pentacoordinate silicates. TBAF in excess was considered to be required for trapping the tetrafluorosilane produced in the catalytic cycle of the cross-coupling reaction.
OXIDATIVE CLEAVAGE OF SILICON-CARBON BONDS IN ORGANOSILICON FLUORIDES TO ALCOHOLS
Tamao, K.,Kakui, T.,Akita, M.,Iwahara, T.,Kanatani, R.,et al.
, p. 983 - 990 (2007/10/02)
Certain functional silyl groups have been shown to be synthetically equivalent to the OH group.All of the C-Si bonds in organosilicon fluorides, K2 and RnSiF4-n (n=1,2,3) are cleaved by m-chloroperbenzoic acid (MCPBA) in DMF to give the corresponding alcohols in high yields.Although the reaction with RSiF5(2-) and RSiF3 proceeds without any additive, cleavage of R2SiF2 and R3SiF requires, respectively, a catalytic or excess amount of KF.A triorganoethoxysilane also undergoes similar oxidative cleavage reactions in the presence of an excess amount of KF.The MCPBA-oxidation of exo- and endo-2-norbornyl-silicate and -trifluorosilane proceeds stereospecifically with retention of configuration at carbon.A remarkable solvent effect has been observed in the oxidative cleavage of RSiF3.A plausible mechanism involves a hexacoordinate silicon species in which the organic group intramolecularly migrates from Si to O of the coordinated MCPBA.
