- Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils
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The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.
- Zhu, Jia-Liang,Tsai, Yi-Ting
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p. 813 - 828
(2020/12/22)
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- METHOD FOR PREPARING 1,3-DICARBONYL COMPOUND BASED ON METAL HYDRIDE/PALLADIUM COMPOUND SYSTEM
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Disclosed is a method for preparing a 1,3-dicarbonyl compound based on a metal hydride/palladium compound system. The method includes the following steps: suspending a palladium compound and a metal hydride in a solvent under the protection of nitrogen, t
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Paragraph 0043-0044
(2021/07/10)
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- APPLICATION OF METAL HYDRIDE/PALLADIUM COMPOUND SYSTEM IN PREPARATION OF 1,3-DICARBONYL COMPOUND IN CASCADE REACTION OF ELECTRON-DEFICIENT ALKENE COMPOUND
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Provided is an application of a metal hydride/palladium compound system in the preparation of a 1,3-dicarbonyl compound in a cascade reaction of an electron-deficient alkene compound, said reaction comprising the following steps: under the protection of n
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Paragraph 0043-0044
(2021/07/10)
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- The Employment of Sodium Hydride as a Michael Donor in Palladium-catalyzed Reductions of α, β-Unsaturated Carbonyl Compounds
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Sodium hydride was employed as a Michael donor under the catalysis of PdCl2 for 1,4-conjugate reductions of α, β-unsaturated carbonyl compounds, which features operational simplicity, mild conditions and high atom-economy. The merits of NaH as a reductant were demonstrated by the one-pot or cascade reactions for the syntheses of complex molecules. (Figure presented.).
- Liu, Ye,Mao, Yujian,Hu, Yanwei,Gui, Jingjing,Wang, Liang,Wang, Wei,Zhang, Shilei
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supporting information
p. 1554 - 1558
(2019/02/16)
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- Method for preparing 1,3-dicarbonyl compound based on metal hydride/palladium compound system
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The invention discloses a method for preparing a 1,3-dicarbonyl compound based on a metal hydride/palladium compound system. The method comprises the following steps: making a palladium compound and metal hydride suspend in a solvent under the protection
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Paragraph 0029
(2019/01/08)
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- Application of metal hydride/ palladium compound system in preparing 1,3-dicarbonyl compound through cascade reaction in electron-deficient alkene compound
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The invention discloses application of a metal hydride/ palladium compound system in preparing a 1,3-dicarbonyl compound through cascade reaction in an electron-deficient alkene compound. The reactioncomprises the following steps of under the protection o
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Paragraph 0029
(2019/01/14)
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- Gold-catalyzed ring-expansion through acyl migration to afford furan-fused polycyclic compounds
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A gold-catalyzed ring-expansion reaction of alkynones to access furan-fused polycyclic compounds is reported. Mechanistic studies revealed that the reaction might occur through a tandem 1,2-acyl migration/Friedel-Crafts reaction.
- Zhang, Changyuan,Jiang, Huanfeng,Zhu, Shifa
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supporting information
p. 2677 - 2680
(2017/03/10)
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- SAR-based optimization of 2-(1H-pyrazol-1-yl)-thiazole derivatives as highly potent EP1 receptor antagonists
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We describe a medicinal chemistry approach for generating a series of 2-(1H-pyrazol-1-yl)thiazoles as EP1 receptor antagonists. To improve the physicochemical properties of compound 1, we investigated its structure-activity relationships (SAR).
- Atobe, Masakazu,Naganuma, Kenji,Kawanishi, Masashi,Morimoto, Akifumi,Kasahara, Ken-Ichi,Ohashi, Shigeki,Suzuki, Hiroko,Hayashi, Takahiko,Miyoshi, Shiro
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p. 6569 - 6576
(2014/01/06)
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- Palladium-catalyzed carbonylative cyclization via trapping of acylpalladium derivatives with internal enolates. Its scope and factors affecting the C-to-O ratio
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The Pd-catalyzed carbonylative cyclization reaction involving ω-acyl-substituted acylpalladium derivatives can proceed via intramolecular trapping with either C- or O-enolates; the preferential formation of either 5- or 6-membered rings dictates the C-to-
- Negishi, El-Ichi,Coperet, Christophe,Sugihara, Takumichi,Shimoyama, Izumi,Zhang, Yantao,Wu, Guangzhong,Tour, James M.
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p. 425 - 436
(2007/10/02)
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