145552-31-4

Upstream product

• 27829-72-7 ethyl (E)-hex-2-enoate 
• 623-73-4 diazoacetic acid ethyl ester 
• 123-72-8 butyraldehyde 
• 28942-46-3 Ethyl 3-chloro-2-oxohexanoate 
• 136805-81-7 ethyl 2-<(p-nitrobenzenesulfonyl)oxy>-3-hydroxyhexanoate 

Downstream Products

• 139619-01-5 (2S,3R)-1-(3,5-Dinitro-benzoyl)-3-propyl-aziridine-2-carboxylic acid ethyl ester 
• 117668-85-6 3-Hydroxy-2-phenylselanyl-hexanoic acid ethyl ester 
• 2305-25-1 3-hydroxy-hexanoic acid ethyl ester 
• 139619-43-5 (4S,5S)-2,2,2-Triphenyl-4-propyl-2λ⁵-[1,3,2]oxazaphospholidine-5-carboxylic acid ethyl ester 
• 139619-44-6 (4S,5S)-2,2,2-Triphenyl-5-propyl-2λ⁵-[1,3,2]oxazaphospholidine-4-carboxylic acid ethyl ester 

Relevant academic research and scientific papers

PROCESS FOR PRODUCTION OF OPTICALLY ACTIVE 3-AMINO-2 -HYDROXYPROPIONIC CYCLOPROPYLAMIDE DERIVATIVES AND SALTS THEREOF

An objective of the present application is to provide an industrially practicable method for producing an optically-active 3-amino-2-hydroxypropionic cyclopropylamide derivative or salt thereof from an inexpensive easily-available starting material. The derivative or salt thereof is useful as an intermediate for a medicine. It is also intended by the present application to provide a useful intermediate of the derivative. The objective is attained by the following method. First, an easily-available 2-halo-3-oxopropionic acid derivative is asymmetrically reduced, and then epoxidated to produce an optically-active epoxycarboxylic acid derivative. Next, the derivative is converted into an optically-active epoxyamide derivative by reaction with cyclopropylamine, and then reacted with a nitrile to obtain an optically-active oxazolinamide derivative. Subsequently, selective acid solvolysis of the oxazoline skeleton gives the optically-active 3-amino-2-hydroxypropionic cyclopropylamide derivative or salt thereof.

Organic reactions catalyzed by methylrhenium trioxide: Reactions of ethyl diazoacetate and organic azides

Methylrhenium trioxide (CH3ReO3 or MTO) catalyzes several classes of reactions of ethyl diazoacetate, EDA. It is the first high valent oxo complex for carbene transfer. Under mild conditions and in the absence of other substrates, EDA was converted to a 9:1 mixture of diethyl maleate and diethyl fumarate. In the presence of alcohols, α-alkoxy ethyl acetates were obtained in good yield. The yields dropped for the larger and more branched alcohols, the balance of material being diethyl maleate and fumarate. An electron-donating group in the para position of phenols favors the formation of α-phenoxy ethyl acetates. The use of EDA to form α-thio ethyl acetates and N-substituted glycine ethyl esters, on the other hand, is hardly affected by the size or structure of the parent thiol or amine, with all of these reactions proceeding in high yield. MTO-catalyzed cycloaddition reactions occur between EDA and aromatic imines, olefins, and carbonyl compounds. Three-membered ring products are formed: aziridines, cyclopropanes, and epoxides, respectively. The reactions favor the formation of trans products, and provide a convenient route for the preparation of aziridines. Intermediate carbenoid and nitrenoid species have been proposed. In the presence of an oxygen source such as an epoxide, ethyl diazoacetate and azibenzil are converted to an oxalic acid monoethyl ester and tobenzil; at the same time the epoxide was converted to an olefin. These results provide further support for the proposed intermediate, a cyclic species containing Re, O, and CHCO2Et (or, occasionally, CPhC(O)Ph)in a three-membered ring.

Stereospecific preparation of glycidic esters from 2-chloro-3-hydroxyesters. Application to the synthesis of (2R,3R)-3-phenylisoserine

Cis- and trans-glycidic esters may be synthesized in high enantiomeric purities by cyclisation with potassium carbonate in DMF of the corresponding syn- or anti-2-chloro-3-hydroxyesters, prepared by microbial reduction of 2-chloro-3-oxoesters. In contrast, more basic media such as sodium ethylate afford exclusively the trans-isomer, whatever the stereochemistry of the starting 2-chloro-3-hydroxyester is. Cyclisation of deuterated compounds showed that this result was due to a rapid isomerisation of the syn esters into anti isomers before cyclisation. An application of this reaction to the synthesis of (2R,3R)-3-phenylisoserine is described.

Highly Enantioselective Reduction of 3-Chloro-2-oxoalkanoates with Fermenting Bakers' Yeast. A New Synthesis of Optically Active 3-Chloro-2-hydroxyalkanoates and Glycidic Esters

Reduction of 3-chloro-2-oxoalkanoic esters with fermenting bakers' yeast gave optically active 3-chloro-2-hydroxyalkanoic esters 2 (anti(2S,3R)/syn(2S,3S) = 52:48-90:10) in 50-85percent yields with > 95percent ee except for 43percent ee of ethyl syn-(2S,3S)-3-chloro-2-hydroxy-4-phenylbutanoate (2j).Compounds 2 were treated with NaOEt to give (E)-(2R,3S)-2,3-epoxyalkanoates 3 in 30-66percent yields with 44-64percent ee.Optically active 2,3-epoxy alcohols (cis-23, trans-23, and trans-25), key intermediates for the syntheses of (-)-disparlure (4), mosquito pheromone (5), and a component of passion fruit flavor (6), were prepared with more than 86percent ee in high yields.

A convenient synthesis of aziridine-2-carboxylic esters

Optically active oxirane-2-carboxylic esters, prepared from allylic alcohols employing the Sharpless epoxidation, were treated with sodium azide.The azido alcohols obtained were subsequently converted into aziridine-2-carboxylic esters by reaction with triphenylphosphine, in good yields and with high optical purity.Various racemic oxirane-2-carboxylic esters were subjected to the same sequence of reactions.

Synthesis and Reactions of 3-Hydroxy-2-nosyloxy Esters Produced by the Stereoselective Reduction of 2-Nosyloxy-3-keto Esters

The reduction of 2-nosyloxy-3-keto esters is an effective method for the preparation of 3-hydroxy-2-nosyloxy esters.The reduction is stereoselective for the syn isomer.The anti isomer can be produced as the major product by the addition of p-nitrobenzenesulfonyl peroxide to ketene bis-silyl acetal derivatives of 3-hydroxy esters.The diastereomers are separable chromatographically and can be converted stereospecifically to glycidic esters and 2-azido-3-hydroxy esters.As such they appear to have excellent potential as versatile synthetic intermediates for the synthesis of 1,2,3-trifunctional substances.