56734-74-8Relevant academic research and scientific papers
"Pseudo-Cationic" Trifluoromethylation of Enol Esters with Sodium Trifluoromethanesulfinate.
Langlois, Bernard R.,Laurent, Eliane,Roidot, Nathalie
, p. 1291 - 1294 (1992)
Enol esters are converted into corresponding trifluoromethylated ketones and/or enol esters with sodium trifluoromethanesulfinate and t-butyl hydroperoxide in the presence of catalytic amounts of Cu(II). Key Words: trifluoromethylation; enol esters; sodiu
Electrochemical Synthesis of Fluorinated Ketones from Enol Acetates and Sodium Perfluoroalkyl Sulfinates
Vil’, Vera A.,Merkulova, Valentina M.,Ilovaisky, Alexey I.,Paveliev, Stanislav A.,Nikishin, Gennady I.,Terent’ev, Alexander O.
supporting information, p. 5107 - 5112 (2021/06/30)
The electrochemical synthesis of fluorinated ketones from enol acetates and RfSO2Na in an undivided cell under constant current conditions was developed. The electrosynthesis proceeded via perfluoroalkyl radical generation from sodium perfluoroalkyl sulfinate followed by addition to the enol acetate and transformation of the resulting C radical to a fluorinated ketone. The method is applicable to a wide range of enol acetates and results in the desired products in yields of 20 to 85%.
Csp3-H Trifluoromethylation of Unactivated Aliphatic Systems
He, Jiachen,Nguyen, Truong N.,Guo, Shuo,Cook, Silas P.
supporting information, p. 702 - 705 (2021/02/01)
A straightforward method for the undirected trifluoromethylation of unactivated methylene units was developed. The reaction proceeds in aqueous acetonitrile with Grushin's reagent, bpyCu(CF3)3, under broad-spectrum white-light irradiation. The trifluoromethylation tolerates a wide range of functional groups including ketones, esters, nitriles, amides, alcohols, and carboxylic acids. The C-H cleavage step is performed via intermolecular H atom abstraction, and the selectivities across a range of methylene units are reported. Mechanistic studies offer a general reaction coordinate for the overall transformation.
Direct C(sp3)?H Trifluoromethylation of Unactivated Alkanes Enabled by Multifunctional Trifluoromethyl Copper Complexes
Choi, Geunho,Lee, Geun Seok,Park, Beomsoon,Kim, Dongwook,Hong, Soon Hyeok
supporting information, p. 5467 - 5474 (2021/01/20)
A mild and operationally simple C(sp3)?H trifluoromethylation method was developed for unactivated alkanes by utilizing a bench-stable CuIII complex, bpyCu(CF3)3, as the initiator of the visible-light photoinduced reaction, the source of a trifluoromethyl radical as a hydrogen atom transfer reagent, and the source of a trifluoromethyl anion for functionalization. The reaction was initiated by the generation of reactive electrophilic carbon-centered CF3 radical through photoinduced homolytic cleavage of bpyCu(CF3)3, followed by hydrogen abstraction from an unactivated C(sp3)?H bond. Comprehensive mechanistic investigations based on a combination of experimental and computational methods suggested that C?CF3 bond formation was enabled by radical–polar crossover and ionic coupling between the resulting carbocation intermediate and the anionic CF3 source. The methylene-selective reaction can be applied to the direct, late-stage trifluoromethylation of natural products and bioactive molecules.
Radical Desulfur-Fragmentation and Reconstruction of Enol Triflates: Facile Access to α-Trifluoromethyl Ketones
Su, Xiaolong,Huang, Honggui,Yuan, Yaofeng,Li, Yi
supporting information, p. 1338 - 1341 (2017/01/24)
We report an efficient oxidative radical desulfur-fragmentation and reconstruction of enol triflates for the synthesis of α-CF3ketones. Preliminary mechanistic studies disclosed that oxidative fragmentation to release a CF3radical fr
Synthesis of α-trifluoromethyl ketones via the Cu-catalyzed trifluoromethylation of silyl enol ethers using an electrophilic trifluoromethylating agent
Li, Lun,Chen, Qing-Yun,Guo, Yong
supporting information, p. 5145 - 5152 (2014/06/23)
A method has been developed for the synthesis of α-trifluoromethyl ketones via the Cu-catalyzed trifluoromethylation of silyl enol ethers with an electrophilic trifluoromethylating agent, which produces a trifluoromethyl radical.
Continuous flow α-trifluoromethylation of ketones by metal-free visible light photoredox catalysis
Cantillo, David,De Frutos, Oscar,Rincon, Juan A,Mateos, Carlos,Kappe, C. Oliver
, p. 896 - 899 (2014/03/21)
A continuous-flow, two-step procedure for the preparation of α-CF3-substituted carbonyl compounds has been developed. The carbonyl substrates were converted in situ into the corresponding silyl enol ethers, mixed with the CF3 radical source, and then irradiated with visible light using a flow reactor based on transparent tubing and a household compact fluorescent lamp. The continuous protocol uses Eosin Y as an inexpensive photoredox catalyst and requires only 20 min to complete the two reaction steps.
Photoredox catalysis: A mild, operationally simple approach to the synthesis of α-trifluoromethyl carbonyl compounds
Pham, Phong V.,Nagib, David A.,MacMillan, David W. C.
supporting information; experimental part, p. 6119 - 6122 (2011/08/05)
A facile and efficient method for the α-trifluoromethylation of carbonyl compounds and enolsilanes has been accomplished through application of a photoredox catalysis strategy. A one-flask procedure for the direct α-trifluoromethylation and α-perfluoroalk
Mechanistic studies on α-trifluoromethylation of ketones via silyl enol ethers and its application to other carbonyl compounds
Sato, Kazuyuki,Yuki, Takashi,Yamaguchi, Ryoji,Hamano, Tetsuya,Tarui, Atsushi,Omote, Masaaki,Kumadaki, Itsumaro,Ando, Akira
supporting information; experimental part, p. 3815 - 3819 (2009/10/01)
(Chemical Equation Presented) Synthesis of α-CF3 carbonyl compounds has been recognized to be difficult up to now because the polarization of CF3δ--Iδ+ is opposite to that of CH3δ+-Iδ-, and this makes it difficult to introduce CF3+ unit to enolates. We recently reported an effective R-trifluoromethylation of ketones by using Et 2Zn with Rh catalyst, but the mechanism has not fully been cleared. Now, we carried out the detailed mechanistic studies and found the involvement of a highly reactive alkylrhodium complex which derived from Et2Zn and RhCl(PPh3)3 in this α-trifluoromethylation. Furthermore, this α-trifluoromethylation was applied to other types of carbonyl compounds in good yields.
Zn-mediated rhodium-catalyzed α-trifluoromethylation of ketones via silyl enol ethers
Sato, Kazuyuki,Yuki, Takashi,Tarui, Atsushi,Omote, Masaaki,Kumadaki, Itsumaro,Ando, Akira
, p. 3558 - 3561 (2008/09/21)
The treatment of silyl enol ethers of ketones with CF3-I and Et2Zn in the presence of RhCl(PPh3)3 in DME gave α-trifluoromethyl ketones in good yields. The reaction can be widely applicable to silyl enol ethers
