111609-50-8Relevant articles and documents
Synergistic Photoredox/Nickel Coupling of Acyl Chlorides with Secondary Alkyltrifluoroborates: Dialkyl Ketone Synthesis
Amani, Javad,Molander, Gary A.
, p. 1856 - 1863 (2017/02/10)
Visible light photoredox/nickel dual catalysis has been employed in the cross-coupling of acyl chlorides with potassium alkyltrifluoroborates. This protocol, based on single-electron-mediated alkyl transfer, circumvents the restriction of using reactive alkylmetallic nucleophiles in transition-metal-catalyzed acylation and achieves a mild and efficient method for the synthesis of unsymmetrical alkyl ketones. In this approach, a variety of acyl chlorides have been successfully coupled with structurally diverse potassium alkyltrifluoroborates, generating the corresponding ketones with good yields.
Friedel–Crafts reactions of acyl trifluoromethanesulfonates and cyclic acylsulfonium cations generated from acyl fluorides
Raghavendra Rao,Vallée, Yannick
, p. 4442 - 4447 (2016/07/06)
Reactive acyl trifluoromethanesulfonates are formed from the reaction of acyl fluorides with trimethylsilyl trifluoromethanesulfonate (TMSOTf). These electrophiles undergo Friedel–Crafts reactions with electron-rich aromatics at room temperature. When a sulfur atom is present at their γ position, their cyclization to acylsulfonium cations is observed and is followed by a rearrangement leading to benzothiepinones (or dibenzo[b,e]thiepinones) in 40–85% yield.
Deprotonative metalation of functionalized aromatics using mixed lithium-cadmium, lithium-indium, and lithium-zinc species
Snegaroff, Katia,L'Helgoual'ch, Jean-Martial,Bentabed-Ababsa, Ghenia,Nguyen, Tan Tai,Chevallier, Floris,Yonehara, Mitsuhiro,Uchiyama, Masanobu,Derdour, Aicha,Mongin, Florence
experimental part, p. 10280 - 10290 (2010/04/24)
In situ mixtures of CdCl2TMEDA (0.5 equiv; TMEDA = N,N,N',N'-tetramethylethylenediamine) or InCl3 (0.33 equiv) with [Li(tmp)] (tmp = 2,2,6,6-tetramethylpiperidino; 1.5 or 1.3 equiv, respectively) were compared with the previously described mixture of ZnCl2-TMEDA (0.5 equiv) and [Li(tmp)] (1.5 equiv) for their ability to deprotonate anisole, benzothiazole, and pyrimidine. [(tmp)3CdLi] proved to be the best base when used in tetrahydrofuran at room temperature, as demonstrated by subsequent trapping with iodine. The Cd-Li base then proved suitable for the metalation of a large range of aromatics including benzenes bearing reactive functional groups (CONEt2, CO2Me, CN, COPh) or heavy halogens (Br, I), and heterocycles (from the furan, thiophene, pyrrole, oxazole, thiazole, pyridine, and diazine series). Fivemembered heterocycles benefiting from doubly activated positions were similarly dideprotonated at room temperature. The aromatic lithium cadmates thus obtained were involved in palladium-catalyzed cross-coupling reactions or simply quenched with acid chlorides.
Ruthenium Complex Catalyzed Intermolecular Hydroacylation and Transhydroformylation of Olefins with Aldehydes
Kondo, Teruyuki,Akazome, Motohiro,Tsuji, Yasushi,Watanabe, Yoshihisa
, p. 1286 - 1291 (2007/10/02)
Low-valent ruthenium complexes such as dodecacarbonyltriruthenium (Ru3(CO)12), (η4-1,5-cyclooctadiene)(η6-1,3,5-cyclooctatriene)ruthenium (Ru(COD)(COT)) and bis(η5-cyclooctadienyl)ruthenium showed high catalytic activity for the intermolecular hydroacylation of olefins with various aromatic and heteroaromatic aldehydes at 180-200 deg C for 24-48 h under an initial carbon monoxide pressure of 20 kg cm-2 to give unsymmetric ketones in moderate to good yields.In the reaction of 2-thiophenecarbaldehyde with cyclohexene, cyclohexyl 2-thienyl ketone was obtained in 62 percent yield.On the other hand, when the aliphatic aldehyde, heptanal, was treated with cyclohexene, the corresponding ketone was not obtained at all, and a transhydroformylation reaction proceeded; i.e., the formyl group of heptanal was apparently transformed to cyclohexene to give cyclohexanecarbaldehyde in 29 percent yield, together with their Tishchenko-type reaction products.
