35258-38-9Relevant academic research and scientific papers
Selective α-Methylation of Aryl Ketones Using Quaternary Ammonium Salts as Solid Methylating Agents
Templ, Johanna,Schnürch, Michael
, p. 4305 - 4315 (2022/03/16)
We describe the use of phenyl trimethylammonium iodide (PhMe3NI) as an alternative methylating agent for introducing a CH3group in α-position to a carbonyl group. Compared to conventional methylating agents, quaternary ammonium salts have the advantages of being nonvolatile, noncancerogenic, and easy-to-handle solids. This regioselective method is characterized by ease of operational setup, use of anisole as green solvent, and yields up to 85%.
Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium saltsviaregioselective Heck arylation at room temperature
Venkatesh, Rapelly,Singh, Adesh Kumar,Lee, Yong Rok,Kandasamy, Jeyakumar
, p. 7832 - 7837 (2021/09/28)
Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing α-aryl indoles and 3-aryl isocoumarin from styryl ethers.
Enantioselective α-Arylation of Ketones via a Novel Cu(I)-Bis(phosphine) Dioxide Catalytic System
Escudero-Casao, Margarita,Licini, Giulia,Orlandi, Manuel
supporting information, p. 3289 - 3294 (2021/04/07)
A novel catalytic system based on copper(I) and chiral bis(phosphine) dioxides is described. This allows the arylation of silyl enol ethers to access enolizable α-arylated ketones in good yields and enantiomeric excess up to 95%. Noncyclic ketones are amenable substrates with this method, which complements other approaches based on palladium catalysis. Optimization of the ligand structure is accomplished via rational design driven by correlation analysis. Preliminary mechanistic hypotheses are also evaluated in order to identify the role of chiral bis(phosphine) dioxides.
Direct Synthesis of Mono-α-arylated Ketones from Alcohols and Olefins via Ni-Catalyzed Oxidative Cross-Coupling
Yang, Peng-Fei,Shu, Wei
supporting information, p. 6203 - 6208 (2020/08/12)
Controlled synthesis of α-monoarylated ketones is significant yet challenging due to the site-selectivity issues and nonproductive overarylation reactions. Herein, we reported the direct synthesis of α-arylated ketones enabled by Ni-catalyzed dehydrogenative cross-coupling reaction cascade between alcohols and olefins. The use of readily available and cost-effective alcohols and olefins provides a straightforward access to monoarylated ketones in good yields with exclusive selectivity without using any advanced synthetic intermediates.
Blue Light Promoted Difluoroalkylation of Aryl Ketones: Synthesis of Quaternary Alkyl Difluorides and Tetrasubstituted Monofluoroalkenes
Li, Kangkui,Chen, Jingchao,Yang, Chunhui,Zhang, Keyang,Pan, Chunxiang,Fan, Baomin,Fan, Baomin
supporting information, p. 4261 - 4265 (2020/06/04)
A facile and cost-effective method for the preparation of fluoroalkylated compounds has been described by the direct photoexcitation of halofluoroalkanes with blue light absorptivity, enabling the difluoroalkylation of aryl ketones. The methodology has provided an efficient, mild, and catalyst-free synthetic method for quaternary difluoroalkylated arenes and tetrasubstituted monofluoroalkenes.
Nickel-Copper-Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes
Ueda, Yusuke,Iwai, Tomohiro,Sawamura, Masaya
supporting information, p. 9410 - 9414 (2019/05/29)
The hydroacylation of vinylarenes with acyl fluorides and hydrosilanes was enabled by a synergistic bimetallic Ni/Cu-catalytic system, giving access to the corresponding branched ketone products. The reaction takes place under mild conditions at 25–80 °C and tolerates base-sensitive functional groups such as methoxycarbonyl and acetoxy groups.
Electrochemical [4+2] Annulation-Rearrangement-Aromatization of Styrenes: Synthesis of Naphthalene Derivatives
Ma, Yueyue,Lv, Jufeng,Liu, Chengyu,Yao, Xiantong,Yan, Guoming,Yu, Wei,Ye, Jinxing
, p. 6756 - 6760 (2019/04/17)
We report the first electrochemical strategy to synthesize functionalized naphthalene derivatives through [4+2] annulation—rearrangement–aromatization from styrenes under mild conditions. The electrolysis does not require metals, oxidants and high valence substrates, indicating the atom and step-economy ideals. The dehydrodimer produced through [4+2] cycloaddition of 4-methoxy α-methyl styrene is isolated and proved to be the key intermediate for the following oxydehydrogenation to form carbon cation, which undergoes rearrangement–aromatization to afford the final products. This reaction represents a powerful access to construct multi-substituted naphthalene blocks in a single step.
N-Heterocyclic carbene-palladacyclic complexes: synthesis, characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides
Liu, Feng,Hu, Yuan-Yuan,Li, Di,Zhou, Quan,Lu, Jian-Mei
, p. 5683 - 5690 (2018/08/24)
N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01 mol%).
One-pot synthesis of α,α-disubstituted Aryl-1-ethanones via the Wittig-Horner reaction
Yang, Yunxia,Wang, Le,Chen, Yuan,Dai, Yiru,Sun, Zhihua
, p. 121 - 126 (2018/01/04)
A one-pot methodology for the synthesis of α,α-disubstituted aryl-1-ethanones via the Wittig-Horner reaction has been developed and described in this manuscript. Both aryl/alkyl and dialkyl α-branched arylethanone were obtained in high yields (up to 96%) without the use of any metal catalysts. A total of 14 α,α-disubstituted arylethanone derivatives were synthesized based on this simple method that easily converts the carbonyl carbon (sp2) into the sp3 carbon. This versatile method is expected to further promote the use of substituted ketones as synthetic building blocks to construct a variety of α-branched aryl ketones.
Metal-free synthesis of ketones by visible-light induced aerobic oxidative radical addition of aryl hydrazines to alkenes
Ding, Ya,Zhang, Wenkai,Li, Hao,Meng, Yunge,Zhang, Te,Chen, Qiu-Yun,Zhu, Chunyin
supporting information, p. 2941 - 2944 (2017/07/24)
A green and cost-effective method has been developed for the conversion of alkenes to ketones under metal-free conditions. The reaction involves the oxidative addition of alkenes with aryl radicals, which are generated by visible-light induced aerobic oxidation of arylhydrazines. The key features of this reaction include broad substrate scope, readily available reagents and amenability to gram-scale synthesis.
