109089-84-1Relevant articles and documents
Isolation and Characterization of Regioisomers of Pyrazole-Based Palladacycles and Their Use in α-Alkylation of Ketones Using Alcohols
Mamidala, Ramesh,Samser, Shaikh,Sharma, Nishant,Lourderaj, Upakarasamy,Venkatasubbaiah, Krishnan
supporting information, p. 3343 - 3351 (2017/09/18)
Regioisomers of 3,5-diphenyl-1-(4-(trifluoromethyl)phenyl)-1H-pyrazole-based palladacycles (1 and 2) were synthesized by the aromatic C-H bond activation of N/3-aryl ring. The application of these regioisomers as catalysts to enable the formation of α-alkylated ketones or quinolines with alcohols using a hydrogen borrowing process is evaluated. Experimental results reveal that palladacycle 2 is superior over palladacycle 1 to catalyze the reaction under similar reaction conditions. The reaction mechanisms for the palladacycles 1 and 2 catalyzed α-alkylation of acetophenone were studied using density functional theoretical (DFT) methods. The DFT studies indicate that palladacycle 2 has an energy barrier lower than that of palladacycle 1 for the alkylation reaction, consistent with the better catalytic activity of palladacycle 2 seen in the experiments. The palladacycle-phosphine system was found to tolerate a wide range of functional groups and serves as an efficient protocol for the synthesis of α-alkylated products under solvent-free conditions. In addition, the synthetic protocol was successfully applied to prepare donepezil, a drug for Alzheimer's disease, from simple starting materials.
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 0040-0043, (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.
Hydrogen-borrowing and interrupted-hydrogen-borrowing reactions of ketones and methanol catalyzed by iridium
Shen, Di,Poole, Darren L.,Shotton, Camilla C.,Kornahrens, Anne F.,Healy, Mark P.,Donohoe, Timothy J.
supporting information, p. 1642 - 1645 (2015/02/05)
Reported herein is the use of catalytic [{Ir(cod)Cl}2] to facilitate hydrogen-borrowing reactions of ketone enolates with methanol at 65°C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pronucleophiles to the reaction mixture allowed a one-pot methylenation/conjugate addition protocol to be developed, which greatly expands the range of products that can be made by this methodology.
Catalyst-free dehydrative α-alkylation of ketones with alcohols: Green and selective autocatalyzed synthesis of alcohols and ketones
Xu, Qing,Chen, Jianhui,Tian, Haiwen,Yuan, Xueqin,Li, Shuangyan,Zhou, Chongkuan,Liu, Jianping
, p. 225 - 229 (2014/01/17)
Direct dehydrative α-alkylation reactions of ketones with alcohols are now realized under simple, practical, and green conditions without using external catalysts. These catalyst-free autocatalyzed alkylation methods can efficiently afford useful alkylated ketone or alcohol products in a one-pot manner and on a large scale by Ci￡C bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Plain and simple: The title reaction has been realized under simple and practical conditions without using external catalysts, and can afford alkylated ketone or alcohol products in a one-pot manner and on a large scale. The reaction proceeds by Ci￡C bond formation of the in situ generated intermediates with subsequent controllable and selective Meerwein-Pondorf-Verley-Oppenauer-type redox processes. Copyright
