109796-89-6Relevant academic research and scientific papers
Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon
Horino, Yoshikazu,Ishibashi, Mayo,Nakasai, Kosuke,Korenaga, Toshinobu
, (2020/08/28)
The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi–Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated.
Investigation of indium phosphide quantum dot nucleation and growth utilizing triarylsilylphosphine precursors
Gary, Dylan C.,Glassy, Benjamin A.,Cossairt, Brandi M.
, p. 1734 - 1744 (2014/03/21)
We have developed a two-phosphine strategy to independently tune nucleation and growth kinetics based on the relative reactivity of each precursor in the synthesis of indium phosphide (InP) quantum dots (QDs). This approach was allowed by the exploration
Linear free-energy relationship and rate study on a silylation-based kinetic resolution: Mechanistic insights
Akhani, Ravish K.,Moore, Maggie I.,Pribyl, Julia G.,Wiskur, Sheryl L.
, p. 2384 - 2396 (2014/04/17)
The substituent effect of different p-substituted triphenylsilyl chlorides on silylation-based kinetic resolutions was explored. Electron-donating groups slow down the reaction rate and improve the selectivity, while electron-withdrawing groups increase the reaction rate and decrease the selectivity. Linear free-energy relationships were found correlating both selectivity factors and initial rates to the σpara Hammett parameters. A weak correlation of selectivity factors to Charton values was also observed when just alkyl substituents were employed but was nonexistent when substituents with more electronic effects were incorporated. The rate data suggest that a significant redistribution of charge occurs in the transition state, with an overall decrease in positive charge. The linear free-energy relationship derived from selectivity factors is best understood by the Hammond postulate. Early and late transition states describe the amount of substrate participation in the transition state and therefore the difference in energy between the diastereomeric transition states of the two enantiomers. This work highlights our efforts toward understanding the mechanism and origin of selectivity in our silylation-based kinetic resolution.
