10407-33-7Relevant articles and documents
Clay catalysis: Storks alkylation and acylation of cyclohexanone without isolation of enamine
Hammadi,Villemin
, p. 2901 - 2904 (1996)
Cyclohexanone and morpholine in the presence of KSF under azeotropic distillation gave 1-morpholinocyclohexane which is alkylated or acylated in situ without isolation of the enamine. The overall yield of these Stork's reactions are better or equivalent to those obtained by isolation of the enamine.
Michael addition of ketone enolates to α,β-unsaturated esters or amides in a one-pot procedure: Highly efficient effect of lithium salt generated in situ on organotin enolate
Yasuda, Makoto,Shigeyoshi, Yusuke,Shibata, Ikuya,Baba, Akio
, p. 233 - 239 (2005)
Michael addition of a metal ketone enolate to an α,β-unsaturated ester is thermodynamically disfavored, and thus, isolated metal enolates with an equimolar amount of Lewis acids or additives are usually required. This work describes the methodology of one
Efficient synthesis of ω-functionalized nonanoic acids
Cotarca,Delogu,Maggioni,Nardelli,Bianchini,Sguassero
, p. 328 - 332 (1997)
Starting from cyclohexanone and acrylonitrile, a four-step synthesis of the title open-chain C9 compounds is reported. An improved protocol for cyanoethylation of cyclohexanone in the presence of a catalytic amount of cyclohexylamine afforded 3-(2-oxocyclohexyl)propanenitrile (1) in 92% yield. Cyclohexaneperoxycarboxylic acid (CHPCA) is introduced as a highly efficient reagent in the Baeyer-Villiger rearrangement of 1, yielding over 90% of 2. Pyrolysis of 2 afforded under optimized conditions 3 in 92% yield and 99% regioisomeric purity, otherwise a mixture of three unsaturated isomeric ω-cyano nonenoic acids 3, 10 and 11 is obtained. Partial hydrogenation of 3 allowed the isolation of 4 in 90% yield. Hydrogenation of 4 at elevated hydrogen pressure gave 9-aminononanoic acid (5), whereas hydrolysis of 4 led to 1,9-nonanedioic acid (azelaic acid, 6). Both, 5 and 6 are valuable C9 monomers for the preparation of polyamides with specific properties.
Room-temperature, acid-catalyzed [2+2] cycloadditions: Suppression of side reactions by using a flow microreactor system
Kurahashi, Kei,Takemoto, Yoshiji,Takasu, Kiyosei
, p. 270 - 273 (2012)
Added value: The [2+2] cycloaddition of silyl enol ethers with α,β-unsaturated esters, catalyzed by the superstrong acid triflic imide (Tf2NH), at room temperature in a flow microreactor system is reported. The micororeactor method achieves the [2+2] cycloaddition of unstable silyl enol ethers and acrylates, which is unsuccessful in batch reactors, even at room temperature. Copyright
Intramolecular Photoaddition of Alkenes to Chiral 1,3-Dioxin-4-ones: Evidence for Effect of Pyramidalization on the Facial Selectivity
Haddad, Nizar,Abramovich, Zehavit
, p. 6883 - 6887 (1995)
Intramolecular photoaddition of alkenes to chiral 1,3-dioxin-4-ones 5 present, for the first time, examples with high facial selectivity in which the addition proceeds preferentially from the less exposed side (b-side) under kinetic control conditions.This unprecedented facial selectivity cannot be explained only on the basis of steric effects; however, it is consistent with the direction of pyramidalization in structure 3.It can be concluded that the geometry of the pyramidalized Cβ in the triplet excited dioxinones plays an important role in defining the facial selectivity in this reaction.However, steric effect cannot be neglected in rationalizing the facial selectivity as found by comparing the facial selectivity obtained in the irradiation of the studied compounds.
A de novo Synthesis of Oxindoles from Cyclohexanone-Derived γ-Keto-Ester Acceptors Using a Desaturative Amination-Cyclization Approach
Caldora, Henry P.,Govaerts, Sebastian,Dighe, Shashikant U.,Turner, Oliver J.,Leonori, Daniele
supporting information, p. 4272 - 4278 (2021/08/13)
Here we report a desaturative approach for oxindole synthesis. This method uses simple ethyl 2-(2-oxocyclohexyl)acetates and primary amine building blocks as coupling partners. A dual photoredox cobalt manifold is used to generate a secondary aniline that, upon heating, cyclizes with the pendent ester functionality. The process operates under mild conditions and was applied to the modification of several amino acids, the blockbuster drug mexiletine, as well as the formation of dihydroquinolinones.
A practical synthetic route to enantiopure 6-substituted cis-decahydroquinolines
Amat, Mercedes,Navio, Laura,Llor, Nuria,Molins, Elies,Bosch, Joan
supporting information; experimental part, p. 210 - 213 (2012/03/10)
Starting from 4-substituted cyclohexanones, a practical synthetic route to enantiopure 6-substituted cis-decahydroquinolines has been developed, the key steps being a stereoselective cyclocondensation of an unsaturated δ-keto ester derivative with (R)-phenylglycinol and the stereoselective hydrogenation of the resulting tricyclic oxazoloquinolone lactams.
Ring contraction/transannular cyclization of chiral bicyclo[3.3.1] nonanediones mediated by thallium(III) nitrate
Kubilius, Rytis,Bagd?inas, Gintautas,Butkus, Eugenijus
experimental part, p. 346 - 348 (2011/02/28)
The reaction of several chiral bicyclo[3.3.1]nonane ketones mediated by thallium(III) nitrate to afford ring contraction products is investigated. The effect of solvent on the oxidation is discussed, and the use of thallium(III) nitrate for the oxidative
Preparation of sixteen 3-hydroxy-4- and 7-hydroxy-1-hydrindanones and 3-hydroxy-4- and 8-hydroxy-1-hydroazulenones
Tsantali, Georgia G.,Dimtsas, John,Tsoleridis, Constantinos A.,Takakis, Ioannis M.
, p. 258 - 265 (2007/10/03)
3-Hydroxyoctahydro-4H-inden-4-ones and 7-hydroxyoctahydro-1H-inden-1-ones (1, 2 and 3, 4, respectively), as well as the homologous 3-hydroxyoctahydro- 4(1H)-azulenones (5, 6) and 8-hydroxyoctahydro-1(2H)-azulenones (7, 8), were prepared diastereoselective
Palladium-catalyzed intramolecular hydroalkylation of alkenyl- β-keto esters, α-aryl ketones, and alkyl ketones in the presence of Me 3SiCl or HCI
Han, Xiaoqing,Wang, Xiang,Pei, Tao,Widenhoefer, Ross A.
, p. 6333 - 6342 (2007/10/03)
Reaction of 3-butenyl β-keto esters or 3-butenyl α-aryl ketones with a catalytic amount of [PdCl2(CH3CN)2] (2) and a stoichiometric amount of Me3SiCl or Me3SiCl/ CuCl2 in dioxane at 25-70°C formed 2-substituted cyclohexanones in good yield with high regioselectivity. This protocol tolerated a number of ester and aryl groups and tolerated substitution at the allylic, enolic, and cis and trans terminal olefinic positions. In situ NMR experiments indicated that the chlorosilane was not directly involved in palladium-catalyzed hydroalkylation, but rather served as a source of HCl, which presumably catalyzes enolization of the ketone. Identification of HCl as the active promoter of palladium-catalyzed hydroalkylation led to the development of an effective protocol for the hydroalkylation of alkyl 3-butenyl ketones that employed sub-stoichiometric amounts of 2, HCl, and CuCl2 in a sealed tube at 70°C.
