18709-01-8Relevant articles and documents
Application of copper(II)-mediated radical cross-dehydrogenative coupling to prepare spirocyclic oxindoles and to a formal total synthesis of Satavaptan
Hurst, Timothy E.,Gorman, Ryan,Drouhin, Pauline,Taylor, Richard J.K.
, p. 6485 - 6496 (2018)
Application of radical cross-dehydrogenative coupling (CDC) procedures to prepare a range of novel spirocyclic oxindoles and to a formal total synthesis of the vasopressin V2 receptor antagonist Satavaptan is reported. The key step involves a c
Electrochemical Carboxylation of Ketones RCOCH2R' Coupled with CO2 Reduction by 2+
Tanaka, Koji,Miyamoto, Hajime,Tanaka, Toshio
, p. 2033 - 2036 (1988)
Electrochemical carboxylation of PhCOCH3 and C6H10(O) coupled with CO2 reduction by 2+ was carried out in CO2-saturated dry CH3CN.CO2 ligated on the ruthenium atom is reduced to HCOO- or CO upon the electrochemical reduction of the complex, where PhCOCH3 and C6H10(O) function as a proton source, and the resultant carbanions react with CO2 to afford the corresponding ketoacids, catalytically.
Mechanism of the Carboxylation of Cyclohexanone with Carbon Dioxide Catalyzed by 1,8-Diazabicycloundec-7-ene
Mori, Hisakazu
, p. 435 - 440 (1988)
The dependence of the rate of carboxylation upon the concentration of the reactant was investigated in dimethyl sulfoxide.The reaction rate depended upon the concentration of cyclohexanone and 1,8-diazabicycloundec-7-ene(DBU) in the first order, re
Ethyl cyclohexanone-2-carboxylate in aqueous micellar solutions. 2: Enol nitrosation in anionic and cationic micelles
Iglesias, Emilia
, p. 10295 - 10302 (2001)
Micellar-mediated rates of both the ester hydrolysis and enol nitrosation reactions of ethyl cyclohexanone-2-carboxylate, ECHC, were measured in aqueous acid media. In equal acid concentration, the enol nitrosation reaction rate is more than 10 times faster than the ester hydrolysis reaction rate; this fact makes possible the separate (independent) study of both reactions undergone by ECHC. Anionic micelles of sodium dodecyl sulfate, SDS, inhibit the ester hydrolysis; by contrast, the nitrosation reaction goes through maxima as the [SDS] increases above the critical micelle concentration. A similar pattern of behavior is observed in the study of the effect of anionic micelles of hydrogen dodecyl sulfate, HDS, on the rates of the two reactions: the first-order rate constant (ko) of the ester hydrolysis goes through minima as [HDS] increases, even though the rates are actually affected very little by HDS addition; in sharp contrast, the overall rate constant of the nitrosation reaction is enhanced by HDS addition and levels off at high surfactant concentration. The values of the rate constant at high surfactant concentration is more than 6 times that determined in the absence of HDS. Despite the different micellar effects observed in the two reactions occurring in the same substrate, experimental data fit the pseudophase ion exchange (PPIE) model and predict similar values for the second-order rate constant of each reaction in the different types of micelles of a given counterion. The implications of these findings for the reactivity in micelles are discussed. Cationic micelles inhibit the nitrosation reaction throughout the surfactant concentration range; although the reaction at the micellar phase is not negligible, the physicochemical properties of this reaction region account for the lower reactivity in this medium. Experimental data are quantitatively explained by means of the pseudophase model, and kinetic rate constants or equilibrium constants appearing in the proposed reaction scheme are reported.
Ethyl cyclohexanone-2-carboxylate in aqueous micellar solutions. 1: Ester hydrolysis in cationic and nonionic micelles
Iglesias, Emilia
, p. 10287 - 10294 (2001)
Hydrolysis rates for the ester of ethyl cyclohexanone-2-carboxylate (ECHC) were measured in aqueous dioxane mixtures and in aqueous micellar solutions of cationic, nonionic, and mixed cationic-nonionic detergents. The following cationic surfactants were used: dodecyltrimethylammonium bromide (DTABr), tetradecyltrimethylammonium bromide (TTABr), tetradecyltrimethylammonium chloride (TTACl), tetradecyltrimethylammonium acetate (TTAAc), and cetyltrimethylammonium bromide (CTABr). Poly(ethylene oxide)-9-dodecyl ether (C12E9) and poly(ethylene oxide)-20-cetyl ether (C16E20) were used as the nonionic surfactants. The kinetic profiles of the reactions were investigated as a function of surfactant concentration. In aqueous strong mineral acid (HCl or HBr) solutions of the cationic surfactants DTABr, TTABr, TTACl, and CTABr, the reaction was greatly inhibited at surfactant concentrations above the critical micelle concentration; the same behavior was observed for the influence of the nonionic surfactants and for the mixed surfactants DTABr + C12E9 analyzed in an equimolar mixture of both surfactants. Micellar effects were analyzed by means of the pseudophase model. When the hydrolysis reaction was studied in aqueous buffered solutions of acetic acid-acetate, the shape of the observed rate constant versus surfactant concentration (of TTACl and TTABr) profiles depended on surfactant concentration. At low surfactant concentration, first-order rate constants pass through maxima with increasing surfactant concentration followed by a gradual but steady decrease in the rate as the surfactant concentration increases further. By contrast, the first-order rate constant increases throughout the whole concentration range of TTAAc used. Micellar effects observed for the reaction in aqueous buffered solutions were analyzed qualitatively or quantitatively by means of the pseudophase ion exchange (PPIE) model. In every experimental situation, the reaction at the micellar interface is not negligible; however, the second-order rate constant in this region is lower than that measured in water.
Enantioselective Synthesis of Medium-Sized-Ring Lactones via Iridium-Catalyzed Z-Retentive Asymmetric Allylic Substitution Reaction
Ding, Lu,Song, Hao,Zheng, Chao,You, Shu-Li
supporting information, p. 4770 - 4775 (2022/03/27)
Medium-sized rings are important structural units, but their synthesis, especially in a highly enantioselective manner, has been a great challenge. Herein we report an enantioselective synthesis of medium-sized-ring lactones by an iridium-catalyzed Z-retentive asymmetric allylic substitution reaction. The reaction features mild conditions and a broad substrate scope. Various eight- to 11-membered-ring lactones can be afforded in moderate to excellent yields (up to 88%) and excellent enantioselectivity (up to 99% ee). The utilization of both Z-allyl precursors and an Ir catalyst is critical for the medium-sized-ring formation.
Design, synthesis, and molecular simulation studies of N-phenyltetrahydroquinazolinones as protoporphyrinogen IX oxidase inhibitors
Liang, Lu,Yu, Shuyi,Li, Qian,Wang, Xia,Wang, Dawei,Xi, Zhen
, (2021/05/03)
Discovering new protoporphyrinogen oxidase (PPO, EC 1.3.3.4) inhibitors is a promising direction for agrochemical research. Herein, we reported the discovery and in silico structure-guided optimization of N-phenyltetrahydroquinazolinones 1 and 2 as new PP
Amide derivative, preparation method of amide derivative, and application of amide derivative to pharmacy
-
Paragraph 0250-0253, (2017/08/30)
The invention provides an amide derivative, a preparation method of the amide derivative, and application of the amide derivative to pharmacy. The amide derivative compound is selected from one of the following structures. The compound can be used for preparing medicines in the fields of local anaesthesia or analgesia. (The formulas are as shown in the description).
Substrate scope in the copper-mediated construction of bis-oxindoles via a double C-H/Ar-H coupling process
Drouhin, Pauline,Hurst, Timothy E.,Whitwood, Adrian C.,Taylor, Richard J.K.
supporting information, p. 7124 - 7136 (2015/03/30)
Abstract The synthesis of bis-oxindoles via the copper(II)-mediated double cyclisation of linear bis-anilides is described. Cu(OAc)2·H2O was identified as an efficient and inexpensive catalyst for this process. In contrast to previous methods, which rely on the synthesis of the central core from existing oxindole building blocks, this new approach focusses on concurrent formation of both oxindole rings from a simple linear precursor, allowing the formation of bis-oxindoles containing a diverse range of cyclic and acyclic linkers using a single synthetic method.
Copper-mediated construction of spirocyclic bis-oxindoles via a double C-H, Ar-H coupling process
Drouhin, Pauline,Hurst, Timothy E.,Whitwood, Adrian C.,Taylor, Richard J.K.
supporting information, p. 4900 - 4903 (2015/04/27)
A double C-H, Ar-H coupling process for the conversion of bis-anilides into spirocyclic bis-oxindoles, enabling the concomitant formation of two all-carbon quaternary centers at oxindole 3-positions in a diastereoselective manner, is described. The optimum cyclization conditions utilize stoichiometric Cu(OAc)2·H2O/KOtBu in DMF at 110 °C and have been applied to prepare a range of structurally diverse bis-spirooxindoles in fair to good yields (28-77%); the method has also been extended to prepare bis-oxindoles linked by a functionalized acyclic carbon chain.
