72284-20-9

Upstream product

• 3699-66-9 ethyl 2-diethoxyphosphorylpropionate 
• 2043-61-0 cyclohexanecarbaldehyde 
• 102191-92-4 tert-butyldimethylsiloxyacetaldehyde 
• 100-52-7 benzaldehyde 
• 17640-03-8 ethyl 2,2-dichloropropionate 
• 1262968-84-2 ethyl 2,3-dibromo-3-cyclohexyl-2-methylpropanoate 
• 2985-33-3 monoethyl methylmalonate 
• 87717-21-3 ethyl α-(diisopropoxyphosphinyl)propionate 
• 535-11-5 Ethyl 2-bromopropionate 
• 535-13-7 2-chloro-propanoic acid, ethyl ester 
• 21382-82-1 (carbethoxyethylidene)triphenylphosphorane 
• 77642-81-0 ethyl 3-cyclohexyl-2,3-epoxy-2-methylpropanoate 
• 302571-65-9 ethyl 2-chloro-3-cyclohexyl-3-hydroxy-2-methylpropanoate 
• 64-17-5 ethanol 

Downstream Products

• 115901-85-4 (S)-3-Cyclohexylidene-2-methyl-propionic acid ethyl ester 
• 115901-86-5 (R)-3-Cyclohexylidene-2-methyl-propionic acid ethyl ester 

Relevant academic research and scientific papers

Asymmetric cyclopentannelation. Chiral auxiliary on the allene

(equation presented) An enantioselective variant of the synthesis of cross-conjugated cyclopentenones, based on D-glucose-derived chiral auxiliaries, is described. Minor modification of the method makes it applicable to the preparation of both enantiomeri

Synthesis of α,β-Disubstituted Acrylates via Galat Reaction

Galat reactions between aldehydes and substituted malonic acids half oxyester were found to be efficiently catalyzed by morpholine in refluxing toluene. This transformation allows the stereoselective synthesis of diverse α,β-disubstituted acrylates in moderate to good yields. This method constitutes an attractive alternative to existing methods in terms of scope and eco-compatibility.

Scalable Preparation of Methylated Ando-Type Horner-Wadsworth-Emmons Reagent

The Horner-Wadsworth-Emmons (HWE) reactions are vital to the chemical synthesis of complex molecules, forging a carbon-carbon double bond in the generation of α,β-unsaturated enoates from aldehydes or ketones. Despite their frequent use, the Z-stereoselective formation of α,β-unsaturated esters from aldehydes have been mostly limited to the use of the commercially available Still-Gennari reagent. Ando developed an alternative reagent to achieve the same formation with less expensive reagents. However, an α-methylated Ando-HWE reagent has remained difficult to prepare, hindering a reliable route to α,β-disubstituted Z-enoates. Here, we report the development of a preparative synthesis of a methylated Ando-HWE reagent for the highly Z-selective HWE reaction. Costing $0.49/mmol, this synthesis is significantly cheaper than the currently available Still-Gennari reagent ($11/mmol, Millipore Sigma 2018). The purification procedure does not require chromatography, with recrystallization as the only purification method, making it highly amenable to large-scale production.

Hantzsch Ester as a Photosensitizer for the Visible-Light-Induced Debromination of Vicinal Dibromo Compounds

The debromination of vicinal dibromo compounds to generate alkenes usually requires harsh reaction conditions and the addition of catalysts. Just recently the visible-light-induced debromination of vicinal dibromo compounds emerged as a possible alternative to commonly used methods, but the substrate scope of this reaction is limited and a photocatalyst is necessary for the successful conversion of the starting compounds. A catalyst-free visible-light-induced debromination of vicinal dibromo compounds with a base-activated Hantzsch ester as photosensitizer is reported. The method has a wide substrate scope and a broad functional-group compatibility.

A convenient synthesis of (E)-α,β-unsaturated esters with total stereoselectivity promoted by catalytic samarium diiodide

Synthesis of (E)-α,β-unsaturated esters in high yields and with total stereoselectivity is achieved from α-halo-β-hydroxy esters promoted by catalytic amounts of SmI2. The starting compounds were easily prepared from α-halo esters and aldehydes as a mixture of stereoisomers. A mechanism is proposed to explain this samarium(II)-promoted catalytic β-elimination reaction. Georg Thieme Verlag Stuttgart.

Solvent-free Horner-Wadsworth-Emmons reaction using DBU

The solvent-free Horner-Wadsworth-Emmons reaction with a variety of aldehydes using 1.5 equiv of DBU gave E-α,β-unsaturated esters and ketones in high yields. The E-selectivity was high and the used DBU was recovered.

Stereoseleetive synthesis of polysubstituted alkenes through a phosphine-mediated three-component system of aldehydes, α-halo carbonyl compounds, and terminal alkenes

A study was conducted to demonstrate stereoselective synthesis of polysubstituted alkenes through a phosphine-mediated three-component system of aldehydes, α-halo carbonyl compounds, and terminal alkenes. Triphenylphosphine, α-halo carbonyl compounds, and methyl acrylate were added to a solution of aldehyde in chloroform or 1-propanol under nitrogen at room temperature. The resulting mixture was stirred at the specified temperature until transformation was completely observed by thin layer chromatography (TLC) analysis. The mixture was cooled to room temperature and purified by column chromatography on silica gel, eluting with petroleum ether/ethyl acetate. The study demonstrated that the first one-pot and three-component reaction of aldehydes, α-haloacetates, and terminal alkenes was developed in the presence of phenylphosphine to produce a wide range of trisubstituted alkenes with significant stereoselectivity.

Stereoselective olefination reactions promoted by Rieke manganese

A study of the advantages of using manganese, an inexpensive and nontoxic metal, to perform stereoselective β-elimination reactions and to promote sequential olefination reactions of aldehydes to obtain α,β- unsaturated esters and amides is presented. Various elimination reactions, all of them characterized by occurring with complete stereoselectivity and in high yields, were performed using active manganese (Mn*) as metalating agent. This ability of manganese has been applied to develop a novel and direct synthesis of (E)-α,β-unsaturated esters or amides and (Z)-α,β-unsaturated α-halo esters and α-choroamides through a Mn*-mediated sequential olefination protocol of aldehydes with dichloro esters or amides and trihalo esters or trichloroamides, respectively. Georg Thieme Verlag Stuttgart.

The first sequential reaction promoted by manganese: Complete stereoselective synthesis of (E)-α,β-unsaturated esters from 2,2-dichloroesters and aldehydes

(Chemical Equation Presented) α,β-Unsaturated esters were obtained with complete control of stereoselectivity utilizing a sequential reaction of dichloroesters with a variety of aldehydes, promoted by active manganese. This methodology is generally applicable, and the C-C double bond can be di- or trisubstituted. A mechanism based on a successive aldol-type reaction/β-elimination is proposed to explain these results.

An efficient synthesis of (E)-α,β-unsaturated ketones and esters with total stereoselectivity by using chromium dichloride

(E)-α,β-Unsaturated ketones 1 or esters 2 can be obtained with complete stereoselectivity by reaction of different 2-chloro-3-hydroxy ketones 3 or esters 4 and CrCl2. A comparative study of the results of synthesis of ketones 1 with CrCl2 or samarium is performed. A mechanism to explain both β-elimination reactions has been proposed.