54885-10-8

Upstream product

• 121-39-1 ethyl 3-phenylglycidate 
• 27593-40-4 tert-butyl 3-phenyloxirane-2-carboxylate 
• 105-48-6 isopropyl chloroacetate 
• 100-52-7 benzaldehyde 
• 65017-34-7 isopropyl 3-phenyloxirane-2-carboxylate 
• 105-39-5 chloroacetic acid ethyl ester 
• 121-39-1 ethyl cis-3-phenylglycidate 
• 2272-55-1 ethyl trans-3-phenyl-1-oxirane-2-carboxylate 

Downstream Products

• 127053-48-9 Methyl (2R^*,3R^*)-3-phenyl-1H-aziridine-2-carboxylate 
• 129866-73-5 (2R,3R)-3-Phenyl-1-(3,3,3-trifluoro-2-methoxy-2-phenyl-propionyl)-aziridine-2-carboxylic acid methyl ester 
• 119628-74-9 trans-(4S^*,5R^*)-2,2,2,4-Tetraphenyl-5-methoxycarbonyl-1,3,2-oxazaphospholidine 
• 99458-15-8 Methyl (2R,3S)-(+)-2-hydroxy-3-azido-3-phenyl-propionate 
• 127053-48-9 rac Methyl (2R^*,3S^*)-3-phenyl-1H-aziridine-2-carboxylate 
• 129939-53-3 Methyl (2R,3R)-3-phenyl-1H-aziridine-2-carboxylate 
• 129939-54-4 methyl (2S,3S)-(+)-3-phenyl-1H-aziridine-2-carboxylate 
• 121-39-1 ethyl cis-3-phenylglycidate 
• 129866-72-4 Methyl (2S,3R)-(-)-2-hydroxy-3-azido-3-phenyl-propionate 
• 129866-73-5 (2S,3S)-3-Phenyl-1-(3,3,3-trifluoro-2-methoxy-2-phenyl-propionyl)-aziridine-2-carboxylic acid methyl ester 
• 119628-74-9 trans-(4R,5S)-2,2,2,4-Tetraphenyl-5-methoxycarbonyl-1,3,2-oxazaphospholidine 
• 119628-74-9 trans-(4S,5R)-2,2,2,4-Tetraphenyl-5-methoxycarbonyl-1,3,2-oxazaphospholidine 
• 119628-74-9 cis-(4S^*,5S^*)-2,2,2,4-Tetraphenyl-5-methoxycarbonyl-1,3,2-oxazaphospholidine 
• 25957-39-5 Sodium Z-3-phenyl oxirane-2-carboxylate 

Relevant academic research and scientific papers

Solid sodium hydroxide - THF, convenient system for synthesis esters of glycidic acids by darzens condensation

Isopropyl- and tert-butylchloroacetate react with carbonyl compounds in the presence of powdered sodium hydroxide in THF, without a catalyst, giving substituted glycidates. The process is applied for preparation of glycidates from ketones, hitherto unavailable by phase-transfer catalyzed Darzens condensation.

Convenient synthesis of t-butyl Z-3-substituted glycidates under conditions of phase-transfer catalysis

Reactions of mixtures of t-butyl E- and Z-3-substituted glycidates 1a-h with 50% aq. sodium hydroxide and a catalyst, benzyltriethylammonium chloride, TEBAC in dichloromethane (phase-transfer catalysis, PTC) led to preferential hydrolysis of the E-isomers to afford pure (90-98%) t-butyl Z-3-substituted glycidates 1a-i in good yields; PTC cleavage of glycidates additionally substituted at C-2, 1g or C-3, 1h,i suggests that an aryl group in the Z isomers hampers attack of HO- on the carbonyl carbon atom. As described in the literature, the diastereoselective PTC synthesis of Z-3-substituted glycidates and glycidonitriles consists of fast hydrolysis of E isomers present in mixtures with Z ones.

Synthesis of enantiomerically pure forms of trans-3-phenylglycidic acid.

Trans-(2R,3S)- and (2S,3R)-3-phenylglycidic acids were obtained as pure crystals. The optical properties and chemical stability were characterized. The absolute configuration of the trans(+)- and trans-(-) isomers was established by means of chemical correlation.

Synthesis of all four homochiral stereoisomers of methyl 3-phenyl-1H-aziridine-2-carboxylate

Sodium -E3-phenylglycidate (±)-2E was prepared using the Darzens' procedure. Classical resolution with 1-phenylethylamine afforded optically pure salts (+)-(2S,3R)-2E and (-)-(2R,3S)-2E. Alternatively, (±)-2E was converted into (±)-2Z by ring opening of ethyl ester (±)1E with hydrogen bromide, followed by recyclization and saponification. Classical resolution of (±)-2Z with ephedrine afforded optically pure salts (+)-(2S,3S)-2Z and (-)-(2R,3R)-2Z Treatment of the four sodium salts with sodium azide followed by esterification gave hydroxy azido esters 3, which were finally converted into the four homochiral stereoisomers of methyl 3-phenyl-1H-aziridine-2-carboxylate 5 in a reaction with triphenylphosphine and subsequent heating of the initially formed oxazaphospholidines 4.