1638677-40-3Relevant academic research and scientific papers
Destabilized Carbocations Caged in Water Microdroplets: Isolation and Real-Time Detection of α-Carbonyl Cation Intermediates
Kumar, Anubhav,Mondal, Supratim,Sandeep,Venugopalan, Paloth,Kumar, Anil,Banerjee, Shibdas
supporting information, p. 3347 - 3352 (2022/03/03)
Over the last 50 years, proposals of α-carbonyl cation intermediates have been driven by chemical intuition and indirect evidence. Recently, wide interest in α-carbonyl cation chemistry has opened new gates to prepare α-functionalized carbonyl compounds. Though these intrinsically unstable carbocations are formed under forcing conditions (e.g., in a strong acid medium), their fleeting existence prohibits direct observation or spectroscopic measurement. We report that high-speed aqueous microdroplets can directly capture α-carbonyl cation intermediates from various reactions (Friedel-Crafts arylation, deoxygenation, and azidation) upon bombarding with the corresponding reaction aliquots. The α-carbonyl cations caged in water droplets are then desorbed to the gas phase, allowing their successful measurement by mass spectrometry. This has also enabled us to simultaneously monitor the relative abundance of the associated precursor, α-carbonyl cation intermediate, and product during the progress of the reaction.
Method for preparing alpha-aryl ketone compound by using palladium complex
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Paragraph 0073-0077, (2021/07/17)
The invention relates to a method for preparing an alpha-aryl ketone compound by using a palladium complex, which comprises the steps of in the presence of alkali, taking ketone and halogenated hydrocarbon as raw materials, taking the palladium complex containing an ortho-carborane benzothiazole structure as a catalyst, and carrying out alpha-halogenation reaction at room temperature to prepare the alpha-aryl ketone compound. Compared with the prior art, the palladium complex containing the ortho-carborane benzothiazole structure is applied to catalysis of the alpha-halogenation reaction of ketone and halogenated hydrocarbon, the alpha-aryl substituted ketone compound is prepared through a one-pot method, synthesis of the alpha-aryl ketone compound at room temperature by using simple, easily available and cheap raw materials is achieved, and the method has the advantages of low catalyst use equivalent, mild reaction conditions, more catalytic substrates, high substrate universality and high yield.
Palladium-catalyzed denitrative α-arylation of ketones with nitroarenes
Li, Zhirong,Peng, Yonggang,Wu, Tao
supporting information, (2021/02/16)
The palladium-catalyzed α-arylation of ketones with readily available nitroarenes and nitroheteroarenes provides access to useful α-aryl and α-heteroaryl ketones. The use of the Pd/ BrettPhos catalysts was critical to achieve high efficiency for these transformations, whereas other catalysts led to decreased yields or no conversions. The intramolecular type substrate was also applied in this methodology and gave a chromone derivative. Polyaromatic carbonyl compounds can be easily obtained by multicomponent tandem reactions, via nucleophilic aromatic substitution (SNAr) or cross-coupling reaction followed by this denitrative arylation. Kinetic experiments show that the electronic effect of nitrobenzenes has a greater effect on the reaction rate than the electronic effect of ketones.
Metal Free, Direct and Selective Deoxygenation of α-Hydroxy Carbonyl Compounds: Access to α,α-Diaryl Carbonyl Compounds
Kumar, Anil,Sandeep,Venugopalan, Paloth
supporting information, (2020/04/27)
An efficient, metal free, direct and selective deoxygenation of α-hydroxy carbonyl compounds is achieved with the aid of catalytic amount of aqueous HClO4 (70 %) and triethylsilane as hydride source. A variety of α-hydroxy-α,α-diaryl carbonyl compounds are selectively deoxygenated to give α,α-diaryl carbonyl compounds in good to excellent yields. Intermediacy of α-keto carbenium ion is proposed on the basis of some control experiments and atmospheric pressure chemical ionization mass spectral analysis.
LIGAND, NICKEL COMPLEX COMPRISING LIGAND, AND REACTION USING NICKEL COMPLEX
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Paragraph 0282; 0338-0341, (2016/10/07)
PROBLEM TO BE SOLVED: To provide a method for directly carrying out arylation, especially α-arylation, of a carbonyl compound or a thiocarbonyl compound by using a more inexpensive phenol derivative and a nickel catalyst, and to provide a novel nickel cat
Nickel-catalyzed α-arylation of ketones with phenol derivatives
Takise, Ryosuke,Muto, Kei,Yamaguchi, Junichiro,Itami, Kenichiro
supporting information, p. 6791 - 6794 (2014/07/08)
The nickel-catalyzed α-arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α-arylketones. For this transformation, 3,4-bis(dicyclohexylphosphino) thiophene (dcypt) was identified as a new, enabling, air-stable ligand for this transformation. The intermediate of an assumed C-O oxidative addition was isolated and characterized by X-ray crystal-structure analysis. The nickel-catalyzed α-arylation of ketones with readily available phenol derivatives (esters and carbamates) provides access to useful α-arylketones. The use of 3,4-bis(dicyclohexylphosphino)thiophene (dcypt) as an air-stable ligand enables this transformation. The intermediate of an assumed C-O oxidative addition was isolated and characterized by X-ray crystal-structure analysis.
