187950-80-7Relevant academic research and scientific papers
Mechanism of metal-carbenoid insertion into the Si-H bond
Landais, Yannick,Parra-Rapado, Liliana,Planchenault, Denis,Weber, Valery
, p. 229 - 232 (1997)
Kinetic investigations on the insertion of metal-carbenoid intermediates into the Si-H bond have been carried out. A kinetic isotope effect of 1.5 was found and the plot of log k(X)/k(H) vs σ for the reaction of arylsilanes with EDA, gave a straight line
A Stereospecific Access to Allylic Systems Using Rhodium(II)-Vinyl Carbenoid Insertion into Si-H, O-H, and N-H Bonds
Bulugahapitiya, Priyadarshanie,Landais, Yannick,Parra-Rapado, Liliana,Planchenault, Denis,Weber, Valery
, p. 1630 - 1641 (2007/10/03)
Rhodium-catalyzed decomposition of α-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding α-silyl, α-hydroxy, α-alkoxy, α-amino, and α-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral α-vinyldiazoesters and Doyle's chiral catalyst Rh2(MEPY)4. In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh2(MEPY)4-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.
