72284-21-0Relevant articles and documents
Scalable Preparation of Methylated Ando-Type Horner-Wadsworth-Emmons Reagent
Bressin, Robert K.,Driscoll, Julia L.,Wang, Yanping,Koide, Kazunori
, p. 274 - 277 (2019)
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.
Synthesis of α,β-Disubstituted Acrylates via Galat Reaction
Xavier, Tania,Condon, Sylvie,Pichon, Christophe,Le Gall, Erwan,Presset, Marc
supporting information, p. 6135 - 6139 (2019/08/28)
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.
Hantzsch Ester as a Photosensitizer for the Visible-Light-Induced Debromination of Vicinal Dibromo Compounds
Chen, Wenxin,Tao, Huachen,Huang, Wenhao,Wang, Guoqiang,Li, Shuhua,Cheng, Xu,Li, Guigen
supporting information, p. 9546 - 9550 (2016/07/14)
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.
Solvent-free Horner-Wadsworth-Emmons reaction using DBU
Ando, Kaori,Yamada, Kyohei
experimental part, p. 3297 - 3299 (2010/07/18)
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.
Z-selective Horner-Wadsworth-Emmons reaction of (α-substituted ethyl (Diarylphosphono)acetates with aldehydes
Ando, Kaori
, p. 8411 - 8416 (2007/10/03)
New Horner-Wadsworth-Emmons reagents, ethyl 2- (diarylphosphono)propionates (2), ethyl 2-(diarylphosphono)hexanoates (3), and ethyl 2-(diarylphosphono)-3-methylbutanoates (4) were prepared by alkylation of ethyl (diarylphosphono)acetates. The reaction of
PHOTODECONJUGAISON ENANTIOSELECTIVE D'ESTERS ET DE LACTONES CONJUGUEES EN PRESENCE D'EPHEDRINE
Henin, Francoise,Mortezaei, Reza,Muzart, Jacques,Pete, Jean-Pierre,Piva, Oliverier
, p. 6171 - 6196 (2007/10/02)
α,β-unsaturated esters and α-alkylidene lactones bearing one γ-hydrogen on the unsaturated chain, were deconjugated by irradiation with UV light (λ=254 nm).When the reaction was carried out in the presence of (+) or (-) ephedrine, an enantioselective C-protonation of the photodienolic intermediate led to the deconjugated ester with an enantiomeric excess up to 30 percent.The scape of the reaction and the configuration of the new asymmetric center are discussed.
