121794-79-4

Upstream product

• 57057-12-2 Phosphoric acid diisopropyl ester 1-p-tolyl-vinyl ester 
• 106-45-6 para-thiocresol 
• 934-72-5 Methyl p-tolyl sulfoxide 
• 38649-20-6 (1R,2S,2S,5R)-2-isopropyl-5-methylcyclohexyl-1-(4'-methylbenzoate) 

Relevant academic research and scientific papers

Solvent-enabled radical selectivities: Controlled syntheses of sulfoxides and sulfides

Controlling selectivity is of central importance to radical chemistry. However, the highly reactive and unstable radical intermediates make this task especially challenging. Herein, a strategy for taming radical redox reactions has been developed, in which solvent-bonding can alter the reactivity of the generated radical intermediates and thereby drastically alter the reaction selectivity at room temperature. Various β-oxy sulfoxides and β-hydroxy sulfides can be facilely obtained, some of which are difficult to synthesize by existing methods. Notably, neither a metal catalyst nor any further additives are necessary in these processes. Solvent selection alters the reactivity of the generated reaction intermediate and drastically switches the reaction selectivity under simple and mild conditions. Various β-oxy sulfoxides and β-hydroxy sulfides could be facilely obtained from readily available starting materials. Importantly, neither a metal catalyst nor an additional additive was necessary in these transformations.

Substituent Effect on the Enantiomer-Differentiating Reaction of Lithiomethyl p-Tolyl Sulfoxide with Meta- or Para-Substituted (R)-(-)-Menthyl Benzoates

Treatment of (R)-(-)-menthyl benzoates, which have a variety of meta- or para-substituents, with 2 equivalents of racemic lithiomethyl p-tolyl sulfoxide displays the feature of an enantiomer-differentiating reaction, affording the corresponding optically active β-keto sulfoxides.The degree and the direction of enantioselectivity were affected by the nature of the substituent on benzene ring.The electron-releasing substituents trend to increase the percente.e. value.The reversal in the configuration with the variation in the substituent which has a high electron-withdrawing p-CN group was also observed.The R/S values thus obtained gave a good correlation with Hammett's ? values (γ = 0.975), affording a negative straight line. based on these observations, a plausible stereochemical course of this reaction has been discussed.

Stereochemical Behavior of Intermediary Compounds in the Amine-Catalyzed Knoevenagel Reaction

Treatment of the active methylene compounds and aldehydes with a catalytic amount of a secondary amine produces thermodynamically stable alkenes, and the intermediary amino compounds are isolated.The reaction involves many reversible steps, and the stereochemistry of products is determined in the elimination step from the intermediary compounds via stable planar carbanions, in which the small difference in the steric requirements of two electron-withdrawing groups is effective.Steric and electronic effects in the intermediates sometimes bring about the carbon-carbon bond fission with recovery of active methylene compounds, and these effects prevent the Knoevenagel reaction from occuring.