70774-50-4

Upstream product

• 186581-53-3 diazomethane 
• 5669-15-8 (+/-)-3-Methyl-3-phenyl-oxirancarbonsaeure 
• 96-32-2 bromoacetic acid methyl ester 
• 98-86-2 acetophenone 
• 96-34-4 methyl chloroacetate 
• 3461-50-5 methyl trans-3-methylcinnamate 
• 67-56-1 methanol 
• 28937-48-6 (Z)-3-methyl-3-phenyloxirane-2-carbonitrile 

Downstream Products

• 91828-63-6 Methyl 2-hydroxy-3-phenyl-3-butenoate 

Relevant academic research and scientific papers

Asymmetric Darzens condensation of ketones with α-chloroacetates by means of (-)-8-phenylmenthyl auxiliary

The Darzens condensation of symmetric and unsymmetric ketones with (-)-8-phenylmenthyl α-chloroacetate diastereoselectively affords glycidic esters in 77-94% de; the stereochemistry [(2R,3R) configuration] of the product is understandable in terms of π-π interaction in the open transition state model.

A general method for synthesis of cis-dicarbonyl epoxides through DBU/LiBr-cocatalyzed cyclization of α,β-dicarbonyl peroxides

A general method for synthesis of cis-dicarbonyl epoxides is developed. The highly diastereoselective cyclization of α,β-dicarbonyl peroxides is achieved by DBU/LiBr cocatalysis. The coordination of lithium ion with two carbonyl groups is proposed for the

A facile preparation of indium enolates and their Reformatsky-and Darzens-type reactions

Indium enolates were readily prepared by transmetalation of lithium enolates with indium trichloride, and were subsequently reacted with aldehydes to give β-hydroxy esters in high yields. Indium α-bromo enolates were also prepared and reacted with carbonyl compounds to give Darzens-type α,β-epoxy carbonyl products. The Royal Society of Chemistry 2000.

Asymmetric induction in Darzens condensation by means of (-)-8-phenylmenthyl and (-)-menthyl auxiliaries

Asymmetric Darzens condensation of benzaldehyde and various ketones has been investigated. The condensation of acetophenone, propiophenone and symmetric ketones with (-)-8-phenylmenthyl halogenoacetates 3a,b afforded the corresponding glycidic esters cis-12, cis-13 and 15-19 in 77-96% de, respectively, as the major products. Aza-Darzens condensation between N-benzylideneaniline and 3a occurred to give the trans-aziridine 21 as the major isomer in >85% de. The stereochemistry of the major diastereoisomers of cis-12 and 18 was confirmed by their conversion into the known optically active diols 22 and 24. The configuration of the major product of cis-12 was determined to be 2R,3R and that of 18 to be 2R. The geometric and disastereofacial selectivities were understandable in terms of the open-chain or non-chelated antiperiplanar transition state model in the initial aldol-type reaction.

REACTION OF 4-SUBSTITUTED BENZALDEHYDES AND ACETOPHENONES WITH CHLOROACETONITRILE

Under conditions of phase-transfer catalysis or in homogeneous solution of potassium tert-butoxide the title compounds give stereoisomeric mixtures of substituted 2,3-epoxy nitriles III and IV.Alkaline hydrolysis of epoxy nitriles IV afforded the corresponding 2-arylpropanals in low yields.On treatment with methanol and potassium carbonate, epoxy nitriles III and IV were converted into epoxy esters in good yields.

Dianions Derived from α-Halo Acids. The Darzens Condensation Revisited

The dianions of α-halo carboxylic acids are readily generated by the addition of the acids to 2 equiv of lithium diisopropylamide at low temperatures.When the mixture warms to room temperature dimeric products are formed.When aldehydes and ketones were added to the cooled solutions of the dianions and the reaction mixtures were allowed to warm to room temperature, followed by acid quench, glycidic acids were formed.The glycidic acids, per se, were often too unstable to be isolated and purified but could be analyzed by conversion to their methyl esters withdiazomethane.When the reactions were quenched prematurely, α-chloro-β-hydroxy carboxylic acids were isolated.Homologated aldehydes and ketones were obtained from the glycidic acids by catalytic and thermal decarboxylation methods.

NEW SYNTHETIC ROUTES TO β-FLUORO β-PHENYLLACTIC ACID DERIVATIVES AND Β-FLUOROCYANOHYDRINS

Alkyl phenyl 2,3-epoxycarboxylates from the well-known Darzens glycidic esters synthesis react under very mild conditions with pyridinium-poly-hydrogen fluoride to give corresponding 3-fluoro 3-phenyllactates in almost quantitative yields with a high regio and stereoselectivity.This method can be applied succesfully to other flycidic derivatives: glycidoamides, glycidonitriles, glycidoiminoesters...The spectrometric properties (IR, NMR) are presented.