106511-65-3Relevant articles and documents
Ligand-tuned cobalt-containing coordination polymers and applications in water
Tao, Rong,Yang, Yike,Zhu, Haiyan,Hu, Xinyu,Wang, Dawei
, p. 8452 - 8461 (2020)
Ligands play a key role in modern catalysis research and occasionally determine whether a reaction will take place under specific conditions, such as in water. In this experiment, ligands containing an indole-based diacid moiety were employed to prepare the corresponding cobalt coordination polymer material (Co-CIA) and porous oval polymer material (Co-NCIA). Interestingly, it was observed that Co-CIA could promote the alkylation of ketones with alcohols and alcohols with alcohols, while Co-NCIA was effective for the synthesis of 1-benzyl-2-aryl-1H-benzo[d]imidazoles from various phenylenediamine and benzyl alcohols through borrowing hydrogen and dehydrogenation strategies. Other mechanism explorations, such as deuterium labeling experiments and a kinetics study, were conducted to better understand Co-CIA and Co-NCIA systems and the related transformations. Our studies provided an efficient method for the development of highly active cobalt coordination polymer materials with excellent recovery performance for dehydrogenation and borrowing hydrogen reactions under water and base-free conditions.
Designed pincer ligand supported Co(ii)-based catalysts for dehydrogenative activation of alcohols: Studies onN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines
Singh, Anshu,Maji, Ankur,Joshi, Mayank,Choudhury, Angshuman R.,Ghosh, Kaushik
, p. 8567 - 8587 (2021/06/30)
Base-metal catalystsCo1,Co2andCo3were synthesized from designed pincer ligandsL1,L2andL3having NNN donor atoms respectively.Co1,Co2andCo3were characterized by IR, UV-Vis. and ESI-MS spectroscopic studies. Single crystal X-ray diffraction studies were investigated to authenticate the molecular structures ofCo1andCo3. CatalystsCo1,Co2andCo3were utilized to study the dehydrogenative activation of alcohols forN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines. Under optimized reaction conditions, a broad range of substrates including alcohols, anilines and ketones were exploited. A series of control experiments forN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines were examined to understand the reaction pathway. ESI-MS spectral studies were investigated to characterize cobalt-alkoxide and cobalt-hydride intermediates. Reduction of styrene by evolved hydrogen gas during the reaction was investigated to authenticate the dehydrogenative nature of the catalysts. Probable reaction pathways were proposed forN-alkylation of amines, α-alkylation of ketones and synthesis of quinolines on the basis of control experiments and detection of reaction intermediates.
Preparation method of novel aromatic ketone compound
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Paragraph 0065-0066, (2020/12/08)
The invention discloses a preparation method of a novel aromatic ketone compound. According to the preparation method, an aromatic carboxylic acid compound and an aromatic olefin compound are used asreaction raw materials, triphenylphosphine is taken as a deoxidizing reagent, Methylenene blue is taken as a photocatalyst, stirring and reacting are carried out at room temperature in an N,N-dimethylacetamide solvent under the irradiation of a white light lamp in a nitrogen atmosphere and under the condition of taking 2,4,6-trimethylpyridine as an alkali, thereby obtaining a target product, namely the aromatic ketone compound. The method has the advantages of mild reaction conditions, simplicity in operation, low cost, convenience in purification, environmental friendliness and the like.
Utility of Organoboron Reagents in Arylation of Cyclopropanols via Chelated Pd(II) Catalysis: Chemoselective Access to β-Aryl Ketones
Ilangovan, Andivelu,Ramar, Thangeswaran,Subbaiah, Murugaiah A. M.
, (2020/07/03)
Organoborane reagents were investigated as coupling partners to cyclopropanol-derived β-ketone enolates in the presence of a chelated Pd(II) catalyst. Efficient coupling of a range of electronically and sterically diverse cyclopropanols and aryl/alkenyl boronic derivatives (39 examples, 65-94% yield) could be achieved with the generation of synthetically important β-aryl ketone intermediates in a chemoselective fashion. This reactivity paradigm, which broadens the scope of aryl donor partners to homoenolates, allows open-flask conditions, water as a cosolvent, and preparation of halogen-bearing β-aryl ketones that are distinct from previous methods. This chelated Pd(II) catalysis appears to be different from the Pd(0) pathway, as evident from deuterium scrambling studies that could reveal differentiating protonolysis of an α-keto carbopalladium complex in the terminal step.
Design and Synthesis of Zirconium-Containing Coordination Polymer Based on Unsymmetric Indolyl Dicarboxylic Acid and Catalytic Application on Borrowing Hydrogen Reaction
Hu, Xinyu,Zhu, Haiyan,Sang, Xinxin,Wang, Dawei
supporting information, p. 4293 - 4300 (2018/10/02)
Catalytic borrowing hydrogen reaction is a very attractive transformation in the field of C-alkylation reaction. In this work, a new Zr (Zirconium)-containing coordination polymer containing unsymmetric indolyl dicarboxylic acid 1-(carboxymethyl)-1H-indole-5-carboxylic acid (H2CIA) was synthesized by the way of a solvothermal synthetic route and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Nitrogen adsorption-desorption, fourier transform infrared spectroscopy and X-ray photoelectronic spectroscopy (XPS). The coordination polymer Zr-CIA was employed as the catalyst for C-alkylation of acetophenone derivatives in the presence of benzyl alcohol. In addition, Zr-CIA catalyst was also observed to be effective in the reaction of alcohols with alcohols and high yields of alkylation products were achieved. Mechanism investigations were also conducted to better understand the catalysts and transformations. Meanwhile, the Zr-CIA could be reused at least five times without a notable decrease in activity and selectivity. (Figure presented.).
BINAP-copper supported by hydrotalcite as an efficient catalyst for the borrowing hydrogen reaction and dehydrogenation cyclization under water or solvent-free conditions
Xu, Zhaojun,Yu, Xiaoli,Sang, Xinxin,Wang, Dawei
supporting information, p. 2571 - 2577 (2018/06/11)
A BINAP-Cu system supported by hydrotalcite has been developed and proved to be a highly efficient catalyst for the atom-efficient and green borrowing hydrogen reaction and dehydrogenative cyclization. This BINAP-Cu complex supported by hydrotalcite is highly air-stable and can be recycled at least five times under solvent-free conditions. Notably, 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives could be synthesized from alcohols in only one step with water as the solvent for the first time. This provided a much greener and efficient catalytic method towards the synthesis of functionalized amines, ketones and 1-benzyl-2-aryl-1H-benzo[d]imidazole derivatives with high yields under water or solvent-free conditions.
Alkylation of Ketones Catalyzed by Bifunctional Iron Complexes: From Mechanistic Understanding to Application
Seck, Charlotte,Mbaye, Mbaye Diagne,Coufourier, Sébastien,Lator, Alexis,Lohier, Jean-Fran?ois,Poater, Albert,Ward, Thomas R.,Gaillard, Sylvain,Renaud, Jean-Luc
, p. 4410 - 4416 (2017/11/20)
Cyclopentadienone iron dicarbonyl complexes were applied in the alkylation of ketones with various aliphatic and aromatic ketones and alcohols via the borrowing hydrogen strategy in mild reaction conditions. DFT calculations and experimental works highlight the role of the transition metal Lewis pairs and the base. These iron complexes demonstrated a broad applicability in mild conditions and extended the scope of substrates.
Method for preparing substituted ketone compound through oxidization, dehydration and alkylation of secondary alcohol
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Paragraph 0084-0087, (2017/02/24)
The invention discloses a method for preparing a substituted ketone compound through oxidization, dehydration and alkylation of secondary alcohol, and by means of the green synthetic method, substituted ketones are prepared from primary alcohol and the secondary alcohol through a dehydration C-alkylation-oxidization cascade reaction with the existence of alkali but without a transitional metal catalyst. According to the method, the alcohols which are low in price, easy to obtain, wide in source, stable and low in toxicity are used as alkylation reagent, common base metal inorganic base is used as an additive, methylbenzene is used as solvent, air is economical and safe oxidant, and the corresponding substituted ketone compound with secondary alcohol beta alkylated is directly synthesized through the dehydration C-alkylation-oxidization cascade reaction. The reaction method and condition are simple, no transitional metal catalyst is need, no inert gas protection is needed, the method is easy to operate, the by-product is water, compared with a precious metal catalyst, the inorganic base which is used is low in price and easy to obtain and can be removed conveniently through washing, and no heavy metal residue exists in the final product. Therefore, the method is wide in application scope and has certain research and industrial application prospect.
Transition-Metal-Free Synthesis of Homo- and Hetero-1,2,4-Triaryl Benzenes by an Unexpected Base-Promoted Dearylative Pathway
Rehan, Mohammad,Maity, Sanjay,Morya, Lalit Kumar,Pal, Kaushik,Ghorai, Prasanta
, p. 7728 - 7732 (2016/07/07)
An unprecedented approach for the synthesis of homo- and hetero-1,2,4-triaryl benzenes has been developed using a simple base-mediated reaction of either α-aryl cinnamyl alcohols or α,γ-di-aryl propanones. The salient feature of this strategy involves the sequential hydride transfer, regiospecific condensation, regiospecific dearylation, and aromatization under metal-free reaction conditions. The synthesis of unsymmetrically substituted triphenylenes by oxidative coupling of the synthesized 1,2,4-triaryl benzenes has also been demonstrated.
A novel transition metal-free conjugate reduction of α,β-unsaturated ketones with tosylhydrazine as a hydrogen source
Zhou, Xiaomeng,Li, Xiaokang,Zhang, Wei,Chen, Junmin
, p. 5137 - 5140 (2015/02/19)
A novel and efficient method has been developed for the chemoselective conjugate reduction of α,β-unsaturated ketones with tosylhydrazine as a hydrogen source to the corresponding saturated ketones in moderate to good yields. The present protocol does not require the use of transition metal, and is efficient being applicable to a wide range of substrates (25 examples).
