101594-58-5Relevant articles and documents
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)
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.
Dual Functionalization of α-Monoboryl Carbanions through Deoxygenative Enolization with Carboxylic Acids
Sun, Wei,Wang, Lu,Xia, Chungu,Liu, Chao
supporting information, p. 5501 - 5505 (2018/04/09)
A dual functionalization of 1,1-diborylalkanes through deoxygenative enolization with carboxylic acids was developed. 1,1-Diborylalkanes were activated by MeLi to generate α-monoboryl carbanions. In situ IR spectroscopy indicated an interaction between carboxylic acid and 1,1-diborylalkane before addition of the activation reagent. Release of the active α-monoboryl carbanion from the masked form was necessary for its reaction with carboxylate to afford enolate species. Electrophilic trapping of enolate species with various electrophiles achieved dual functionalization of 1,1-diborylalkanes to afford a variety of α-mono, di-, and tri-substituted ketones.
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.