78120-34-0

Upstream product

• 626-34-6 ethyl aminocrotonate 
• 141-97-9 ethyl acetoacetate 
• 55-21-0 benzamide 
• 98-88-4 benzoyl chloride 
• 623-70-1 ethyl (E)-crotonate 
• 626-34-6 ethyl 3-aminobut-2-enoate 

Downstream Products

• 4620-52-4 Ethyl 4-methyl-2-phenyloxazole-5-carboxylate 
• 78120-45-3 (Z)-3-Thiobenzoylamino-but-2-enoic acid ethyl ester 
• 78120-47-5 (E)-3-Thiobenzoylamino-but-2-enoic acid ethyl ester 

Relevant academic research and scientific papers

Development of practical rhodium phosphine catalysts for the hydrogenation of β-dehydroamino acid derivatives

The rhodium-catalyzed asymmetric hydrogenation of various β-dehydroamino acid derivatives to give optically active β-amino acids has been examined. Chiral monodentate 4,5-dihydro-3H-dinaphthophosphepines, which are easily tuned and accessible in a multi-10-g scale, have been used as ligands. The enantioselectivity is largely dependent on the nature of the substituent at the phosphorous atom and on the structure of the substrate. Applying optimized conditions up to 94% ee was achieved.

Highly efficient and facile synthesis of β-enaminones catalyzed by diphenylammonium triflate

Abstract: The catalytic performance of diphenylammonium triflates as an organocatalyst in the synthesis of β-enaminones from various substituted β-diketones and amides (or amines) were evaluated. A wide range of β-enaminones were efficiently synthesized in good to excellent yields under mild reaction conditions. Applying diphenylammonium triflate (DPAT) as catalyst makes this protocol cost-effective, low corrosive and easy to handle. Graphic abstract: [Figure not available: see fulltext.].

Hydrogen-bond-directed highly stereoselective synthesis of Z-enamides via Pd-catalyzed oxidative amidation of conjugated olefins

An efficient procedure for the preparation of Z-enamides has been developed, involving the reaction of primary amides with conjugated olefins using a Pd/Cu cocatalyst system. It was found that certain additives, such as phosphine oxides and phosphonates, increase the efficiency of the reaction in nonpolar solvents under an oxygen atmosphere, thus producing a variety of Z-enamides in high yields with excellent stereoselectivity under Wacker-type conditions. The oxidative amidation reaction has a broad substrate scope, allowing alkyl, aryl, and vinyl amides to react with olefins conjugated with ester, amide, phosphonate, and ketone groups. The notable preference for the formation of Z-enamides is presumably due to the presence of an intramolecular hydrogen bond between the amido proton and the carbonyl oxygen. The energy difference between two plausible σ-alkylamidopalladium intermediates, leading to Z- and E-isomeric enamide products, respectively, was calculated to be 4.18 kcal/mol. The β-hydride elimination step is assumed to be a stereochemistry-determining step in the overall oxidative amidation process, with the energy level for the transition state leading to the Z-enamide being 5.35 kcal/mol lower than that leading to the E-isomer. The efficiency of photoisomerization between Z- and E-enamides was observed to be largely dependent on the substrates' substituents, and certain E-enamides could be obtained in synthetically useful yields by photoirradiation of Z-isomers. Synthetic application of the present method was successfully demonstrated by a direct formal synthesis of cis-CJ-15,801.

Observation of two oxa-azabicyclohexenone intermediates along the reaction pathway of the photochemical isomerization of 1,3-oxazin-6-ones

Irradiation of 4-methyl-2-phenyl-1,3-oxazin-6-one, 1, yields a photochemical equilibrium between 1 and 2-methyl-4-phenyl-1,3-oxazin-6-one, 2.The isomerization proceeds through two intermediates, the oxa-azabicyclohexenones 3 and 4, both of which can be observed spectroscopically (ir, uv, 1H nmr) at low temperature.

ENAMINE CHEMISTRY, PART XXI. N- AND/OR C-SUBSTITUTION (ALKYLATION, ACYLATION) OF ETHYL 3-AMINO-2-BUTENOATE. THE PREPARATION OF 2-SUBSTITUTED 4-METHYL-1,3-THIAZINE-6-THIONES

Alkylation of ethyl 3-amino-2-butenoate, 1, with methyl iodide, ethyl iodide, and benzyl bromide gave both C- and N-alkylated products (contrary to earlier findings) the ratio of which was determined by GLC.Methylation of 1 was studied under different con

The crystal structure of ethyl-Z-3-amino-2-benzoyl-2-butenoate and measurement of the barrier to E,Z-isomerization

Ethyl-3-amino-2-benzoyl-2-butenoate crystallizes from pentane as either the E (mp 82-84 deg C) or the Z-isomer (mp 95.5-96.5 deg C).The E isomer is less stable, and changes spontaneously into the Z, which has been identified by X-ray crystallography.The structure is characterised by an N-H/ester CO hydrogen bond and a very long C2-C3 bond (1.39 Angstroem).Nuclear magnetic resonance methods have been used to measure the rate of ZE isomerization at several temperatures, leading to the estimate that the free energy of activation at 268 K is 56+/-8 kJ.