102092-51-3Relevant academic research and scientific papers
STUDIES IN TRIFLUOROMETHANESULPHONIC ACID-IV KINETICS AND MECHANISM OF ACYLATION OF AROMATIC COMPOUNDS
Roberts, R. M. G.,Sadri, A. R.
, p. 137 - 142 (1983)
A detailed kinetic study has been made of acylation reactions in solvent trifluoromethane sulphonic acid (CF3SO3H) using carboxylic acids as the electrophilic species involved.These species were shown to be probably the protonated form of the mixed anhydride.The reactions show high substrate selectivity characterised by high negative values of p+.Substituents in the carboxylic acids have a relatively small influence on the reactions rates due to a cancellation of substituents effects on the protonation of the mixed anhydride with those operating on the subsequent slow reaction of these species with the aromatic substrate.Anomalous effects were found for certain ortho substituents.The overall mechanism is discussed in terms of polar and steric effects in conjunction with the competing protonation of the aromatic bases, together with evidence from isotope effects.
Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
Sun, Nan,Sun, Qingxia,Zhao, Wei,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
, p. 2117 - 2123 (2019/03/28)
A new method for the synthesis of diaryl and heterodiaryl ketones has been established based on the palladium-catalyzed carbonylative Suzuki coupling approach with sub-stoichiometric Mo(CO)6 as CO source. Using 0.5 mol% of Pd(TFA)2 as catalyst, 0.5 equivalent of Mo(CO)6 as solid carbonyl reagent and 3 equivalent of K3PO4 as base, a wide range of functionalized (hetero)aryl iodides and (hetero)aryl boronic acids could smoothly proceed the carbonylative cross-coupling reaction in aqueous CH3CN at 50 °C, affording the corresponding ketones in good to excellent yields. The newly developed method was easy to operate under mild conditions with high efficiency. (Figure presented.).
Ni/Ti Dual Catalytic Cross-Coupling of Nitriles and Organobromides to Access Ketones
Chenniappan, Vinoth Kumar,Silwal, Sajan,Rahaim, Ronald J.
, p. 4539 - 4544 (2018/05/23)
Herein, we report the development of a dual catalytic approach for the cross-coupling of nitriles with aryl- and aliphatic-bromides. A titanium(III) catalyst is used to activate nitriles enabling their coupling with organobromides through a nickel catalyst. The Ni/Ti system efficiently prepared unsymmetrical ketones with good chemoselectivity and could selectively couple a bromide in the presence of other functionalizable handles.
Palladium(II)-catalyzed desulfitative synthesis of aryl ketones from sodium arylsulfinates and nitriles: Scope, limitations, and mechanistic studies
Skillinghaug, Bobo,Sk?ld, Christian,Rydfjord, Jonas,Svensson, Fredrik,Behrends, Malte,S?vmarker, Jonas,Sj?berg, Per J. R.,Larhed, Mats
, p. 12018 - 12032 (2015/01/16)
A fast and efficient protocol for the palladium(II)-catalyzed production of aryl ketones from sodium arylsulfinates and various organic nitriles under controlled microwave irradiation has been developed. The wide scope of the reaction has been demonstrated by combining 14 sodium arylsulfinates and 21 nitriles to give 55 examples of aryl ketones. One additional example illustrated that, through the choice of the nitrile reactant, benzofurans are also accessible. The reaction mechanism was investigated by electrospray ionization mass spectrometry and DFT calculations. The desulfitative synthesis of aryl ketones from nitriles was also compared to the corresponding transformation starting from benzoic acids. Comparison of the energy profiles indicates that the free energy requirement for decarboxylation of 2,6-dimethoxybenzoic acid and especially benzoic acid is higher than the corresponding desulfitative process for generating the key aryl palladium intermediate. The palladium(II) intermediates detected by ESI-MS and the DFT calculations provide a detailed understanding of the catalytic cycle. (Figure Presented).
Design, synthesis, and biological evaluation of potent thiosemicarbazone based cathepsin L inhibitors
Kishore Kumar,Chavarria, Gustavo E.,Charlton-Sevcik, Amanda K.,Arispe, Wara M.,MacDonough, Matthew T.,Strecker, Tracy E.,Chen, Shen-En,Siim, Bronwyn G.,Chaplin, David J.,Trawick, Mary Lynn,Pinney, Kevin G.
supporting information; experimental part, p. 1415 - 1419 (2010/07/06)
A small library of 36 functionalized benzophenone thiosemicarbazone analogs has been prepared by chemical synthesis and evaluated for their ability to inhibit the cysteine proteases cathepsin L and cathepsin B. Inhibitors of cathepsins L and B have the potential to limit or arrest cancer metastasis. The six most active inhibitors of cathepsin L (IC50 50 > 10,000 nM). The most active analog in the series, 3-bromophenyl-2′-fluorophenyl thiosemicarbazone 1, also efficiently inhibits cell invasion of the DU-145 human prostate cancer cell line.
Generation of bromophenyllithium reagents from dibromobenzenes and addition to carbonyl and nitrile electrophiles
Caron, Stéphane,Do, Nga M.
, p. 1440 - 1442 (2007/10/03)
An evaluation of the mono-lithiation of all three regioisomers of dibromobenzene using n-butylithium was performed. The resulting aryllithium reagents were added to electrophiles such as ketones, aldehydes, nitriles and amides to afford the desired benzylic alcohols or ketones.
