79852-25-8Relevant academic research and scientific papers
Cross-Coupling of Secondary Amides with Tertiary Amides: The Use of Tertiary Amides as Surrogates of Alkyl Carbanions for Ketone Synthesis
Wang, Shu-Ren,Huang, Pei-Qiang
, p. 887 - 891 (2019/07/18)
In recent years, exciting progress has been made in the field of direct transformation of amides, nevertheless, the condensation between two amides remains rare and restricted to homo-coupling reactions. Herein, we report the cross-coupling of secondary amides with tertiary amides, which provides a synthesis of ketones under mild conditions, and features the use of tertiary amides as surrogates of alkyl carbanions. The method relies on the coupling of enamines, generated from tertiary amides by catalytic partial reduction of tertiary amides with Vaska's catalyst, with nitrilium ions, formed in situ from secondary amides via activation with trifluoromethanesulfonic anhydride, and on the subsequent deformylation.
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.
Preparation of acylthiophenes by iron(III) chloride catalyzed reactions of tris(2-thienyl)stibanes with acyl chlorides
Kakusawa, Naoki,Nakagawa, Yoshie,Toshima, Yutarou,Yasuike, Shuji,Kurita, Jyoji
, p. 1170 - 1175 (2015/07/15)
The reactions of tris(2-thienyl)stibanes with various acyl chlorides, using a catalytic amount of iron(III) chloride, afforded 2-acylthiophenes. Iron(III) chloride is presumed to act as a Lewis acid, and the ipso substituent of each 2-thienyl group of tris(2-thienyl)stibane is replaced with an acyl group. The reaction is highly atom-efficient in that all three thiophene rings of tris(2-thienyl)stibane take part in the reaction. The reaction procedure is so simple that it can also be carried out under solvent-free and aerobic conditions.
Phase-vanishing method: Friedel-Crafts acylation of thiophene with tin tetrachloride and its application to convenient parallel synthesis
Matsubara, Hiroshi,Yasuda, Shinji,Ryu, Ilhyong
, p. 247 - 249 (2007/10/03)
Phase-vanishing (PV) method was applied to Friedel-Crafts acylations of aromatic compounds with tin tetrachloride as a Lewis acid. The reaction proceeded smoothly and acylation products were obtained in good yield. Parallel, four different Friedel-Crafts acylation reactions were carried out successfully based on the present PV method.
A convenient preparation of unsymmetrical ketones from borinates using phase transfer catalysis
Guo, Feng,Huang, Shiwen,Shan, Zixing,Zhao, Dejie
, p. 280 - 281 (2007/10/03)
Unsymmetrical ketones were prepared from borinates via the insertion of dichlorocarbene into the C-B bond under solid-liquid phase transfer catalysis conditions and oxidation with alkaline hydrogen peroxide in 50-78% yields.
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.
