- Modifying Electronic Communication in Dimolybdenum Units by Linkage Isomers of Bridged Oxamidate Dianions
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Reactions of Mo2(O2CCH3)(DAniF) 3, DAniF = N, N′-di-p-anisylformamidinate, with oxamidate dianions [ArNC(O)C(O)NAr]2-, Ar = C6H5 and p-anisyl, give pairs of isomeric compounds where the [Mo2] units are bridged by the oxamidate anions. For the α isomers, the C-C unit of the dianion is nearly perpendicular to the Mo-Mo bonds, and these are essentially perpendicular to each other. For the β isomers, the corresponding C-C unit and the Mo-Mo bonds are essentially parallel to each other. Each type of isomer is stable in solution. The electronic communication as measured by the ΔE1/2 for the oxidation of each of the Mo2 units is significantly better for the β isomers. This is supported also by the appearance of what is conventionally called an intervalence charge-transfer band in the near infrared region upon oxidation of the β isomers but not the α isomers. Molecular mechanics and DFT calculations help explain the relative conformations in the α isomers and the relative energy differences between the α and β isomers.
- Cotton, F. Albert,Liu, Chun Y.,Murillo, Carlos A.,Villagran, Dino,Wang, Xiaoping
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Read Online
- Copper-Catalyzed Ullmann-Type Coupling and Decarboxylation Cascade of Arylhalides with Malonates to Access α-Aryl Esters
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We have developed a high-efficiency and practical Cu-catalyzed cross-coupling to directly construct versatile α-aryl-esters by utilizing readily available aryl bromides (or chlorides) and malonates. These gram-scale approaches occur with turnovers of up to 1560 and are smoothly conducted by the usage of a low catalyst loading, a new available ligand, and a green solvent. A variety of functional groups are tolerated, and the application occurs with α-aryl-esters to access nonsteroidal anti-inflammatory drugs (NSAIDs) on the gram scale.
- Cheng, Fei,Chen, Tao,Huang, Yin-Qiu,Li, Jia-Wei,Zhou, Chen,Xiao, Xiao,Chen, Fen-Er
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p. 115 - 120
(2022/01/04)
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- Visible-light-induced direct construction of amide bond from carboxylic acids with amines in aqueous solution
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A novel visible-light-promoted N-acylation for the synthesis of amides from easily available carboxylic acids with amines in the presence of I2 within 2.5 h in aqueous solution has been developed. Using sunlight as the visible light source greatly reduces the cost of experiments and produces almost no toxic effects. Hence, this study provides an alternative catalytic system for the construction of a wide range of amides with readily available materials. Moreover, the strategy was successfully applied in the preparation of N-(3-(2,6-dimethoxyphenoxy)-7-nitroquinoxalin-2-yl)benzohydrazide, which displayed a signification anti-proliferation effect on A549, MCF-7 and HCT116 cell lines.
- Wang, Jin,Hou, Huiqing,Hu, Yongzhi,Lin, Jin,Wu, Min,Zheng, Zhiqiang,Xu, Xiuzhi
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supporting information
(2021/02/09)
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- N,N′-bis(substituted-phenyl)oxamides and their dinuclear pentacoordinate nickel(II) complexes
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The preparation, spectroscopic characterization and magnetic study of N,N′-bis(substituted-phenyl)oxamidate-bridged nickel(II) dinuclear complexes of formula {[Ni(N3-mc)]2(μ-CONC6H4-X)}(PF6)2/su
- Santana, M. Dolores,García, Gabriel,Vicente-Hernández, Consuelo,García, Luís,Pérez, José,Rojo, Teófilo,Lezama, Luís
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p. 2009 - 2016
(2008/09/19)
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- A new synthesis of bis-enaminones via acylation of ketones
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A short and efficient synthesis for a series of 1,6-diaryl-3,4- diarylaminohexa-2,4-diene-1,6-diones was developed. Based on the acylation-prototropism sequence during the reaction of various aryl methyl ketones with bis-imidoyl chlorides, the products were isolated in good yields. Substituted acetophenones, acetylthiophene, 3-acetylpyridine, and acetylferrocene can be integrated into this reaction as ketone component. Similarly, α-tetralone can be transformed with bis-electrophiles into the corresponding bis-enaminones. Treatment of 2-acetylpyridine with N,N′-bis(4-tolyl)ethanebis(imidoyl) dichloride yielded not only the expected bis-enaminone, but also a new quinolizine derivative which was structurally characterized by single crystal X-ray analysis. Analogously, pinacolone and cyclopropyl methyl ketone can readily be converted into bis-enaminones. Monoimidoyl chlorides showed the same reactivity, providing derivatives in high yields. Georg Thieme Verlag Stuttgart.
- Buehrdel, Gunther,Beckert, Rainer,Petrlikova, Eva,Herzigova, Petra,Klimesova, Vera,Fleischhauer, Jan,Goerls, Helmar
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experimental part
p. 3071 - 3080
(2009/04/06)
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- Method for the synthesis of amides and related products from esters or ester-like compounds
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A versatile, eco-friendly, and efficient method for the convenient conversion of esters and ester-like compounds into amides, peptides, carbamates, ureas, oxamides, oxamates, hydrazides, oxazolidinones, pyrazolones, oxazolidinediones, barbituric acids, and other molecules containing one or more OCN moieties in the presence of a diol or polyol is disclosed.
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Page/Page column 13
(2008/06/13)
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- A new class of near-infrared electrochromic oxamide-based dinuclear ruthenium complexes
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(Chemical equation presented) We report the synthesis of a new class of symmetric and unsymmetric oxamide-based dinuclear ruthenium complexes. These complexes were characterized by NMR, ESI-MS, and electrochemical methods. Spectroelectrochemical analysis of the complexes showed broad absorptions in the NIR region for the mixed-valence state of the complexes. The introduction of a chiral group into the bridging ligand produced an optically active complex that was studied using circular dichroism.
- Rastegar, Majid F.,Todd, Erin K.,Tang, Hongding,Wang, Zhi Yuan
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p. 4519 - 4522
(2007/10/03)
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