50447-68-2Relevant articles and documents
Organomagnesium Based Flash Chemistry: Continuous Flow Generation and Utilization of Halomethylmagnesium Intermediates
Von Keutz, Timo,Cantillo, David,Kappe, C. Oliver
supporting information, p. 7537 - 7541 (2020/10/12)
The generation of highly unstable chloromethylmagnesium chloride in a continuous flow reactor and its reaction with aldehydes and ketones is reported. With this strategy, chlorohydrins and epoxides were synthesized within a total residence time of only 2.6 s. The outcome of the reaction can be tuned by simply using either a basic or an acidic quench. Very good to excellent isolated yields, up to 97%, have been obtained for most cases (30 examples).
Catalytic Enantioselective Conversion of Epoxides to Thiiranes
Liao, Saihu,Leutzsch, Markus,Monaco, Mattia Riccardo,List, Benjamin
supporting information, p. 5230 - 5233 (2016/05/19)
A highly efficient and enantioselective Br?nsted acid catalyzed conversion of epoxides to thiiranes has been developed. The reaction proceeds in a kinetic resolution, furnishing both epoxide and thiirane in high yields and enantiomeric purity. Heterodimer formation between the catalyst and sulfur donor affords an effective way to prevent catalyst decomposition and enables catalyst loadings as low as 0.01 mol %.
Epoxidation of styrenes by hydrogen peroxide as catalyzed by methylrhenium trioxide
Al-Ajlouni, Ahmad M.,Espenson, James H.
, p. 9243 - 9250 (2007/10/03)
Methylrhenium trioxide, CH3ReO3, catalyzes the oxidation of styrenes by hydrogen peroxide. Kinetic studies by three methods were carried out in acidic CH3CN/H2O (1:1 v/v) solutions. The catalytically-active species are the mono-peroxide, CH3Re(O)2(C2), A, and the bis-peroxide, CH3Re(O)(O2)2, B, which epoxidize a given styrene at a similar rate. The rate constants are relatively insensitive to steric hindrance, but increase with the nucleophilicity of the styrene, electron-donating groups on the olefinic carbons or on the aromatic ring enhancing the rate. The rate constants for meta- and para-substituted styrenes follow a linear Hammett relationship; correlation with σ+ gave ρ + -0.93 ± 0.05. In CD3CN, epoxides were observed by 1H NMR spectroscopy. ais-β-Methylstyrene and transβ-methylstyrene led to the cis epoxide and the trans epoxide, respectively. In acidic CH3CN/H2O, the major products were 1,2-diols. In some cases C-C bond cleavage products were also observed, the extreme case being β-methoxystyrene where the C-C bond was completely cleaved to yield benzaldehyde, formaldehyde, and methanol.
