10321-71-8Relevant articles and documents
SiO2 catalysed expedient synthesis of [E]-3-alkenoic acids in dry media
Kumar, H.M. Sampath,Reddy, B.V. Subba,Reddy, E. Jagan,Yadav
, p. 2401 - 2404 (1999)
Aliphatic aldehydes with α-hydrogens and malonic acid undergo decarboxylative condensation on the surface of SiO2 when subjected to microwave irradiation generating βγ-unsaturated acids in high yields.
β-alanine-DBU: A highly efficient catalytic system for knoevenagel-doebner reaction under mild conditions
Zhu, Lingjian,Lei, Ning,Miao, Zhenyuan,Sheng, Chunquan,Zhuang, Chunlin,Yao, Jianzhong,Zhang, Wannian
, p. 139 - 143 (2012)
A mild and efficient Knoevenagel-Doebner reaction from malonic acid and a wide range of aldehydes was catalyzed by a catalytic system consisting of β-alanine and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), affording the corresponding (E)-α,β-unsaturated carboxylic acids in good to excellent yields and with high stereoselectivity. The advantage of the method is that the reaction could proceed smoothly at ambient temperature so that it can tolerate a variety of functional groups and avoid unnecessary side reactions. Copyright
Base-Catalyzed Reactions of α,β-Unsaturated Esters and Nitriles. 4. Dimerization of β-Alkyl-Substituted Acrylates
Shabtai, Joseph,Ney-Igner, Eva
, p. 3795 - 3802 (1981)
2-Butenoates 1-C4 alkyl, cyclohexyl, or 1-bornyl> and higher β-alkyl-substituted acrylates 2-C9 n-alkyl> undergo highly selective (>95percent) dimerization in the presence of promoted potassium or sodium catalysts to yield corresponding 2-alkylidene-3-alkylglutarates (3).The reaction involves metalation of the β-alkylacrylate at the C-2 position, followed by addition at C-3 of a second monomeric molecule.Changes in the relative extent of dimerization (Kr) as a function of structural and experimentalvariables were determined.Kr is strongly dependent upon the inductive and steric characteristics of the alcoholic (R) group and of the β-alkyl substituent (R').For an n-alkyl group as R' the Kr value increases with increase in chain length from C1 to C4 but then decreases for longer substituents (C5-C9).Among the two geometric isomers in the dimeric product 3, the isomer with an α-vinylic hydrogen cis to the carboalkoxy group is predominant in all cases, but its relative concetration decreases with an increase in the size of R'.Branched or cyclic β-substituents in 2 prevent dimerization due to steric hindrance in the rate-determining addition step.Promoted potassium or sodium catalysts show much higher dimerization activity compared to supported alkali metals or to alkoxides.For conversions of up to 60percent, Kr values in proton-exchanging alkylbenzene solvents and in nonexchanging alkylcyclohexanes are closely similar, indicating faster abstraction of an α-vinylic hydrogen from the monomer, rather than a benzylic hydrogen from the solvent, in the chain regeneration step of the reaction.
Studies in Decarboxylation. Part 13. The Incursion of a Stepwise Mechanism in the Gas-phase Decarboxylation of Cyclopropylacetic Acids
Bigley, David B.,Fetter, Clive L.,Clarke, Michael J.
, p. 553 - 556 (1980)
The cyclopropylacetic acids (I)-(IV) have been decarboxylated in the temperature range 720-820 K.It is demonstrated that at 725 K, 2',2'-dimethylcyclopropylacetic acid is decarboxylated by both concerted and stepwise mechanisms.The latter is favoured by higher temperature.Cyclopropylacetic acid is decarboxylated by the concerted mechanism at 725 K, but also exhibits the stepwise mechanism at higher temperature.
MODIFIED KNOEVENAGEL CONDENSATIONS. SYNTHESIS OF (E)-3-ALKENOIC ACIDS.
Ragoussis, Nikitas
, p. 93 - 96 (1987)
Condensation of aliphatic aldehydes with a three molar excess of malonic acid and 0.001 mole piperidinium acetate in refluxing xylene, with continuous removal of the water formed, gave almost exclusively (E)-3-alkenoic acids, in good yield (60-85percent) and of high stereochemical purity (95-99percent).
Inhibitors of Thermus thermophilus isopropylmalate dehydrogenase
Pirrung,Han,Ludwig
, p. 2430 - 2436 (1994)
In an attempt to use mechanism-based design for the discovery of inhibitors of the isopropylmalate dehydrogenase from T. thermophilus, we have prepared and studied a number of potential mimics for an intermediate in the oxidative decarboxylation of isopropyl malate, the enol or enolate of α-ketoisocaproate. Because hydroxamate and dicarboxylate enolate mimics are strong, uncompetitive inhibitors of the enzyme and vinyl fluoride enol mimics are weak, competitive inhibitors, it is suggested that the reaction involves the enolate. The uncompetitive inhibition by a number of anionic compounds suggests, in combination with previous studies in other laboratories, that they mimic the enolate product of the decarboxylation. An explanation for the potency of the inhibition of IMDH by these compounds is proposed based on the electrostatic interaction of product and cofactor.
Palladium-Catalyzed Low Pressure Carbonylation of Allylic Alcohols by Catalytic Anhydride Activation
Schelwies, Mathias,Paciello, Rocco,Pelzer, Ralf,Siegel, Wolfgang,Breuer, Michael
, p. 9263 - 9266 (2021)
A direct carbonylation of allylic alcohols has been realized for the first time with high catalyst activity at low pressure of CO (10 bar). The procedure is described in detail for the carbonylation of E-nerolidol, an important step in a new BASF-route to (?)-ambrox. Key to high activities in the allylic alcohol carbonylation is the finding that catalytic amounts of carboxylic anhydride activate the substrate and are constantly regenerated with carbon monoxide under the reaction conditions. The identified reaction conditions are transferrable to other substrates as well.
Enantioselective conjugate addition of a lithium ester enolate catalyzed by chiral lithium amides
Duguet, Nicolas,Harrison-Marchand, Anne,Maddaluno, Jacques,Tomioka, Kiyoshi
, p. 5745 - 5748 (2006)
(Diagram presented) Mixed aggregates of chiral lithium amide and lithium ester enolate have been employed in the enantioselective conjugate addition on α,β-unsaturated esters. Michael adducts were obtained in ee's up to 76% combining a lithium enolate and a chiral 3-aminopyrrolidine lithium amide. The sense of the induction was found to be determined by both the relative configuration of the stereogenic centers borne by the amide and the solvent in which the reaction was conducted.
Chemoselective γ-Oxidation of β,γ-Unsaturated Amides with TEMPO
Heindl, Sebastian,Lemmerer, Miran,Malzer, Nicolas,Matyasovsky, Ján,Maulide, Nuno,Riomet, Margaux
, p. 19123 - 19127 (2021)
A chemoselective and robust protocol for the γ-oxidation of β,γ-unsaturated amides is reported. In this method, electrophilic amide activation, in a rare application to unsaturated amides, enables a regioselective reaction with TEMPO resulting in the title products. Radical cyclisation reactions and oxidation of the synthesised products highlight the synthetic utility of the products obtained.
COVALENT RAS INHIBITORS AND USES THEREOF
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Page/Page column 155, (2021/06/04)
The disclosure features compounds, or pharmaceutically acceptable salts thereof, alone and in combination with other therapeutic agents, pharmaceutical compositions, and protein conjugates thereof, capable of modulating biological processes including Ras, and their uses in the treatment of cancers.
