916166-24-0Relevant academic research and scientific papers
A facile synthesis of 5,5-dideutero-4-dimethyl(phenyl)silyl-6-undecyl- tetrahydropyran-2-one as a deuterium labeled synthon for (-)-tetrahydrolipstatin and (+)-δ-hexadecanolide
Wagh, Sandip J.,Chowdhury, Raghunath,Mukhopadhyay, Sulekha,Ghosh, Sunil K.
, p. 649 - 654 (2014/01/06)
Deuterium-labeled biologically active compounds are gaining importance because they can be utilized as tracers or surrogate compounds to understand the mechanism of action, absorption, distribution, metabolism, and excretion. Deuterated drug molecules (heavy drugs) become novel as well as popular because of better stability and bioavailability compared with their hydrogen analogs. Labeling of organic molecules with deuterium at specific positions is thus gaining popularity. In this work, we have exploited a highly regioselective and enantioselective direct Michael addition of methyl-d3 alkyl ketones to dimethyl(phenyl)silylmethylene malonate that was catalyzed by (S)-N-(2-pyrrolidinylmethyl)pyrrolidine/trifluoroacetic acid/ D2O combination with high yield and isotopic purity. The 5,5-dideutero-4- dimethyl(phenyl)silyl-6-undecyl-tetrahydropyran-2-one was obtained from the adduct of methyl-d3 undecanyl ketone and dimethyl(phenyl) silylmethylene malonate by a silicon controlled diastereoselective ketone reduction, lactonization, and deethoxycarbonylation. The dideuterated silylated tetrahydropyran-2-one is the precursor for geminal 2H 2-labeled (+)-4-hydroxy-6-undecyl-tetrahydropyran-2-one, an advanced intermediate for gem-dideutero (-)-tetrahydrolipstatin and (+)-δ- hexadecanolide syntheses. Copyright
Triethylgallium as a nonnucleophilic base to generate enolates from ketones
Nishimura, Yoshio,Miyake, Yutaka,Amemiya, Ryo,Yamaguchi, Masahiko
, p. 5077 - 5080 (2007/10/03)
(Chemical Equation Presented) Triethylgallium deprotonated cyclic and acyclic ketones at 125-175°C without forming carbonyl addition products, and the resulting gallium enolates underwent facile C-benzoylation and an aldol reaction. Unsymmetrical ketones were preferentially enolized at the methylene moiety, which was under kinetic control.
