77772-23-7Relevant academic research and scientific papers
Carbene X[sbnd]H bond insertions catalyzed by copper(I) macrocyclic pyridine-containing ligand (PcL) complexes
Tseberlidis, Giorgio,Caselli, Alessandro,Vicente, Rubén
, p. 1 - 5 (2017)
A catalytic system comprising copper(I) and macrocyclic pyridine-containing ligands (Pc-L) proves capable of promoting carbene Si[sbnd]H bond insertions using diazo compounds as the carbene source. This catalytic system showed broad scope and a remarkable robustness as indicated by high TON numbers (up to 30000). Moreover, the use of enynones as carbene sources proved also feasible in hydrosilane insertion using this catalytic system. Finally, the insertion in O[sbnd]H and N[sbnd]H bonds of phenols and anilines, respectively, has been also demonstrated.
Methyldiphenylsilylation of Ester and Lactone Enolates
Larson, Gerald L.,Maldonado, Veronica Cruz de,Fuentes, Lelia M.,Torres, Luz E.
, p. 633 - 639 (2007/10/02)
The reactions of a variety of ester and lactone enolates with methyldiphenylchlorosilane were studied.The C-versus O-silylation, leading to the α-silyl ester or lactone and silyl ketene acetal, respectively, was studied as a function of the structure of the ester or lactone and the reaction conditions.It was found that all simple acetates are C-silylated irrespective of the steric demands of the alcohol portion of the ester.Esters that are monosubstituted in the α-position are cleanly C-silylated with the notable exceptions of ethyl phenylacetate and ethyl phenoxyacetate, both of which give mixtures of C- and O-silylation.The α,α-disubstituted esters give only O-silylation, but the α,α-substituted α-silyl esters are readily prepared by the alkylation of the appropriate monosubstituted α-silylated ester.The reaction of the lithium enolate of ethyl acetate and tert-butyl acetate with (S)-(-)-1-naphthylphenylmethylchlorosilane showed the reaction to occur with inversion of configuration at silicon.Methylation of tert-butyl (1-naphthylphenylmethylsilyl)acetate gave a 91:9 mixture of diastereomeric α-silyl propionates, which could not be separated.It was found that only the γ-lactones gave C-silylation with δ-valerolactone and ε-caprolactone giving O-silylation.
