14737-94-1Relevant academic research and scientific papers
Triethylamine-promoted elimination from (R,R)-PhCHORCHClCO2Me (R = MeCO, PhCO, 4-MeC6H4, 4-MeOC6H4, MeSO2 and 4-MeC6H4SO2) in various solvents
Montani, Rosana S.,Gil, Elisabet,Cabaleiro, Mercedes C.
, p. 138 - 139 (1999)
The rates and stereochemistry of elimination from a number of (R,R)- PhCHORCHClCO2Me (R = MeCO, PhCO, 4-MeC6H4, 4-MeOC6H4, MeSO2 and 4- MeC6H4SO2) with trie
One-Step Preparation of α-Chloro-α,β-unsaturated Carbonyl Compounds by the Reaction of Silyl Enol Ethers with TiCl4-LiAlH4-CCl4
Mitani, Michiharu,Kobayashi, Yoshinori
, p. 284 - 286 (1994)
Reaction of silyl enol ethers in a system composed of TiCl4, LiAlH4, and CCl4, which generates dichlorocarbene, produced α-chloro-α,β-unsaturated carbonyl compounds in an one-step process.
Visible light-mediated metal-free double bond deuteration of substituted phenylalkenes
Iakovenko, Roman,Hlavá?, Jan
supporting information, p. 440 - 446 (2021/01/28)
Various bromophenylalkenes were reductively photodebrominated by using 1,3-dimethyl-2-phenyl-1H-benzo-[d]imidazoline (DMBI) and 9,10-dicyanoanthracene. With deuterated DMBI analogs (the most effective was DMBI-d11), satisfactory to excellent isotopic yields were obtained. DMBI-d11 could also be regenerated from the reaction mixtures with a recovery rate of up to 50%. The combination of the photodebromination reaction with conventional methods for bromoalkene synthesis enables sequential monodeuteration of a double bond without the necessity of a metal catalyst. This journal is
Titanium mediated olefination of aldehydes with α-haloacetates: An exceptionally stereoselective and general approach to (Z)-α-haloacrylates
Augustine, John Kallikat,Bombrun, Agnes,Venkatachaliah, Srinivasa,Jothi, Anandh
, p. 8065 - 8072 (2013/12/04)
An exceptionally stereoselective and general synthesis of (Z)-α-haloacrylates, ready to undergo various synthetic transformations, has been demonstrated from α-haloacetates and aldehydes in a one-pot manner via the titanium-enolate based asymmetric aldol
Ru-catalyzed highly chemo- and enantioselective hydrogenation of γ-halo-γ,δ-unsaturated-β-keto esters under neutral conditions
Ma, Xin,Li, Wanfang,Li, Xiaoming,Tao, Xiaoming,Fan, Weizheng,Xie, Xiaomin,Ayad, Tahar,Ratovelomanana-Vidal, Virginie,Zhang, Zhaoguo
supporting information; experimental part, p. 5352 - 5354 (2012/06/30)
Finely-tuned ruthenium-catalyzed highly chemoselective and enantioselective hydrogenation of γ-halo-γ,δ-unsaturated-β-keto esters at the carbonyl group was achieved under neutral reaction conditions (ee up to 97%). Both olefin and alkenyl halogen moieties, which are labile under hydrogenation conditions, remained untouched during the reaction.
A substrate-driven approach to determine reactivities of α,β-unsaturated carboxylic esters towards asymmetric bioreduction
Tasnádi, Gábor,Winkler, Christoph K.,Clay, Dorina,Sultana, Nargis,Fabian, Walter M. F.,Hall, Mélanie,Ditrich, Klaus,Faber, Kurt
supporting information; experimental part, p. 10362 - 10367 (2012/10/08)
The degree of C=C bond activation in the asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases was studied, and general recommendations to render these "borderline-substrates" more reactive towards enzymatic reduction are proposed. The concept of "supported substrate activation" was developed. In general, an additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates, and α-cyano groups showed little effect. The alcohol moiety of the ester functionality was found to have a strong influence on the reaction rate. Overall, activities were determined by both steric and electronic effects. Biotransformation: The asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases could be tuned by varying the degree of C=C bond activation (see scheme). An additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates. Copyright
Biocatalyzed enantioselective reduction of activated C=C bonds: Synthesis of enantiomerically enriched α-halo-β-arylpropionic acids
Brenna, Elisabetta,Gatti, Francesco G.,Manfredi, Alessia,Monti, Daniela,Parmeggiani, Fabio
experimental part, p. 4015 - 4022 (2011/09/15)
The enantioselective biocatalyzed reduction of the C=C bond of some (Z)-methyl α-halo-β-arylacrylates was investigated. The reaction was performed by baker's yeast fermentation and Old Yellow Enzymes 1-3 mediated biotransformations. The final products wer
Pd0-Catalyzed carbonylation of 1,1-dichloro-1-alkenes, a new selective access to Z-α-chloroacrylates
Arthuis, Martin,Lecup, Anne,Roulland, Emmanuel
supporting information; experimental part, p. 7810 - 7812 (2010/11/18)
A novel and fully chemo- and stereoselective three component strategy leading to Z-α-chloroacrylates by a Pd0-catalyzed reaction of CO (1 atm) with 1,1-dichloro-1-alkenes and various alcohols is disclosed. This catalytic approach compares favourably with the Wittig type strategies as α-chloroacrylates of pure Z configuration are obtained in high yield. The Royal Society of Chemistry.
One-pot synthesis of (E)-a-chloro-a,β-unsaturated esters
Karama, Usama
experimental part, p. 405 - 406 (2009/12/25)
Chlorination of a phosphonate anion derived in situ from methyl bis(2,2,2-trifluoroethoxylphosphonoacetate 2 followed by the addition of aldehydes constitutes a stereoselective single flask procedure for the preparation of E-configured a-chloro-a,β-unsatu
N-heterocyclic carbenes of indazole: Ring enlargement reactions by α-halo ketones and dehalogenations of vicinal dihalides
Schmidt, Andreas,Snovydovych, Bohdan,Gjikaj, Mimoza
experimental part, p. 2798 - 2804 (2009/04/05)
On decarboxylation, 1,2-dimethylindazolium-3-carboxylate forms the N-heterocyclic carbene, 1,2-dimethylindazol-3-ylidene, which deprotonates α-halo ketones. The resulting indazolium salt and the corresponding enolate form 1:1 adducts which undergo a ring enlargement to cinnolines. Reaction with 2-bromo-2,3-dihydro-1H-inden-1-one gives a 4- hydroxyspiro[cinnoline-3,2′-inden]-1′-one by ring enlargement reaction (X-ray crystal structure analysis). Vicinal dibromides undergo debromination under these conditions to give alkenes, and substrates with 1,2-dibromoethene partial structure give acetylenes. As 3-bromoindazole is found as the second product of this reaction, an E1cb mechanism, initiated by Br+ abstraction by the N-heterocyclic carbene of indazole, is suggested. Georg Thieme Verlag Stuttgart.
