835-86-9

Upstream product

• 582-25-2 Potassium benzoate 
• 84028-89-7 ethyl (R)-2-trifluoromethylsulfonyloxypropanoate 
• 766-76-7 benzoate 
• 535-11-5 Ethyl 2-bromopropionate 
• 57057-80-4 ethyl (S)-2-[[(4-methylphenyl)sulfonyl]oxy]propanoate 
• 65-85-0 benzoic acid 
• 63696-99-1 (S)-ethyl 2-(methylsulfonyloxy)propanoate 
• 687-47-8 (S)-Ethyl lactate 

Relevant academic research and scientific papers

A Direct Approach to Enantiopure Propionate Derivatives from Ethyl Lactate

The S-propargyl xanthate derived from ethyl (S)-lactate reacts upon heating with various acidic substances to give the propionate transfer product in high yield and with complete inversion of configuration.

Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents

Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reaction and will be applicable to practical synthesis.

Nucleophilic Substitution Reactions of (Alkoxymethylene)dimethylammonium Chloride

The use of imidate esters as potential replacements for diethyl azodicarboxylate and triphenylphosphine in the Mitsunobu reaction is described. A series of secondary alcohols were allowed to react with (chloromethylene)dimethylammonium chloride, generated from dimethylformamide (DMF) and oxalyl chloride, to give imidate esters. Reaction of these salts with potassium benzoate or potassium phthalimide gave the products of SN2 substitution in excellent yields with clean inversion of stereochemistry. Optimization of reaction conditions is discussed as a means to increase the atom economy of the process by minimizing the quantity of nucleophile required.

CsF in organic synthesis. Inversion of secondary mesylates and tosylates

Clean inversion of secondary mesylates and tosylates is effected by CsF in DMF. A variety of oxygen-, sulfur-, nitrogen-, and carbon-nucleophiles are employable. The reaction conditions have been optimized. The use of CsF in DMF is crucial and the reaction proceeds on the surface of solid CsF. It is suggested that hydrogen bonding between CsF and an active hydrogen of nucleophiles is responsible for the smooth reaction. Cesium carbonate fails to give rise to high specificity of inversion indicative of superiority of CsF.

Substitution of 2-(Sulfonyloxy)carboxylates with Oxygene and Sulfur Nucleophiles without Racemization

The ethyl 2-(sulfonyloxy)propionates (S)-1a-c react with phenolates formed from 2 and with carboxylates 8 to give the respective 2-(aryloxy)- (R)-3 and 2-(acyloxy)propionates (R)-9 with inversion of configuration.Due to the high leaving tendency of the triflate group, (S)-1a generally give higher yields of substitution products under milder conditions than the corresponding mesylate (S)-1b and tosylate (S)-1c.In the case of the reaction of malic and succinic acid derivatives only the triflate (S)-10a is converted to the acyloxy compounds (R)-12 with carboxylates 8 atlow temperature (-45 deg C); with the mesylates 10b and the bromide 10d only elimination is observed.Mercaptides and thiophenolates formed from 17 react with (S)-1a-c analogously.With potassium thiocyanate 1a,b react almost exclusively to give the thiocyanate 19; only traces of the corresponding isothiocyanate 20 are obtained.

PHASE TRANSFER CATALYSIS USING CHIRAL CATALYSTS. V. ASYMMETRIC NUCLEOPHILIC SUBSTITUTIONS WITH C, O, N AND S-ANIONS

Several asymmetric nucleophilic substitutions with C, N, O and S-anions have been performed under PTC conditions using chiral quaternary ammonium salts as PT catalysts.