1121-18-2Relevant articles and documents
PALLADIUM-CATALYZED SYNTHESIS OF α,β-UNSATURATED KETONES FROM KETONES VIA ALLYL ENOL CARBONATES
Shimizu, Isao,Minami, Ichiro,Tsuji, Jiro
, p. 1797 - 1800 (1983)
Allyl enol carbonates, prepared by quenching ketone enolates with allyl chloroformate, are converted to α,β-unsaturated ketones with Pd(OAc)2-dppe catalyst in CH3CN.
Wiberg,Koch
, p. 1779 (1966)
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Rinne et al.
, p. 5759 (1950)
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Conia,J.M.,Barnier,J.P.
, p. 2679 - 2680 (1969)
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ENONE FORMATION FROM ALLYL β-KETO ESTERS ALKENYL ELLYL CARBONATES, SILYL ENOL ETHERS, AND ENOL ACETATES BY THE PHOSPHINE-FREE PALLADIUM CATALYST
Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao,Kataoka, Hideaki
, p. 1133 - 1136 (1984)
The effect of phosphine ligands on the palladium catalyzed enone formation from allyl β-keto esters, alkenyl allyl carbonates, silyl enol ethers, and enol acetates has been reinvestigated, and clean enone formation was observed by a phosphine-free palladium catalyst.
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Friedrich,E.C.,Jassawalla,J.D.C.
, p. 4224 - 4229 (1979)
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ONE-STEP SYNTHESIS OF α,β-UNSATURATED KETONES BY THE REACTION OF ENOL ACETATES WITH ALLYL METHYL CARBONATE CATALYZED BY PALLADIUM AND TIN COMPOUNDS
Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
, p. 5639 - 5640 (1983)
Enol acetates derived from saturated ketones are converted to α,β-unsaturated ketones by heating with allyl methyl carbonate in MeCN by bimetallic catalysis of palladiumphosphine complex and tin methoxide.
Improved robustness of heterogeneous Fe-non-heme oxidation catalysts: A catalytic and EPR study
Bilis,Stathi,Mavrogiorgou,Deligiannakis,Louloudi
, p. 376 - 389 (2014)
There is currently a rarity in production and in-depth catalytic study of heterogeneous non-heme Fe catalysts. Herein, two heterogeneous catalysts have been synthesized by covalent grafting of non-heme Fe-complexes, DPEIFe IIICl and HFEIFeIIICl, on SiO2. The catalytic performance of the obtained DPEIFeIII@SiO2 and HFEIFe III@SiO2 materials has been systematically studied for catalytic oxidation of cyclohexene. The catalytic data show that the present non-heme Fe catalysts are functional and can achieve higher activity compared to other non-heme Fe reported so far in the literature. Importantly, the heterogeneneous catalysts show a remarkable robustness and improved oxidative stability vs. the homogeneous ones. Studies by UV-vis and EPR reveal a common mechanistic pattern: CH3CN interacts with the Fe-atom promoting the formation of a Low-Spin (S = 1/2) intermediate, in the presence of H 2O2, probably a FeIII-OOH hydroperoxide. The role of radical intermediates was investigated in detail by spin-trapping techniques. Finally, taking into account the nature of oxidation products, a consistent catalytic mechanism, valid for both homogeneous and heterogeneous catalysts, is discussed.
Jung et al.
, p. 3961 (1977)
CeO2-Supported Pd(II)-on-Au Nanoparticle Catalyst for Aerobic Selective α,β-Desaturation of Carbonyl Compounds Applicable to Cyclohexanones
Jin, Xiongjie,Mizuno, Noritaka,Takei, Daisuke,Yabe, Tomohiro,Yamaguchi, Kazuya,Yatabe, Takafumi
, p. 5057 - 5063 (2020/05/27)
Direct selective desaturation of carbonyl compounds to synthesize α,β-unsaturated carbonyl compounds represents an environmentally benign alternative to classical stepwise procedures. In this study, we designed an ideal CeO2-supported Pd(II)-on-Au nanoparticle catalyst (Pd/Au/CeO2) and successfully achieved heterogeneously catalyzed selective desaturation of cyclohexanones to cyclohexenones using O2 in air as the oxidant. Besides cyclohexenones, various bioactive enones can also be synthesized from the corresponding saturated ketones under open air conditions in the presence of Pd/Au/CeO2. Preliminary mechanistic studies revealed that α-C-H bond cleavage in the substrates is the turnover-limiting step of this desaturation reaction.
Combining Photo-Organo Redox- and Enzyme Catalysis Facilitates Asymmetric C-H Bond Functionalization
Zhang, Wuyuan,Fueyo, Elena Fernandez,Hollmann, Frank,Martin, Laura Leemans,Pesic, Milja,Wardenga, Rainer,H?hne, Matthias,Schmidt, Sandy
supporting information, p. 80 - 84 (2019/01/04)
In this study, we combined photo-organo redox catalysis and biocatalysis to achieve asymmetric C–H bond functionalization of simple alkane starting materials. The photo-organo catalyst anthraquinone sulfate (SAS) was employed to oxyfunctionalise alkanes to aldehydes and ketones. We coupled this light-driven reaction with asymmetric enzymatic functionalisations to yield chiral hydroxynitriles, amines, acyloins and α-chiral ketones with up to 99 % ee. In addition, we demonstrate functional group interconversion to alcohols, esters and carboxylic acids. The transformations can be performed as concurrent tandem reactions. We identified the degradation of substrates and inhibition of the biocatalysts as limiting factors affecting compatibility, due to reactive oxygen species generated in the photocatalytic step. These incompatibilities were addressed by reaction engineering, such as applying a two-phase system or temporal and spatial separation of the catalysts. Using a selection of eleven starting alkanes, one photo-organo catalyst and 8 diverse biocatalysts, we synthesized 26 products and report for the model compounds benzoin and mandelonitrile > 97 % ee at gram scale.
