459-52-9Relevant academic research and scientific papers
Halogenation through Deoxygenation of Alcohols and Aldehydes
Chen, Jia,Lin, Jin-Hong,Xiao, Ji-Chang
, p. 3061 - 3064 (2018)
An efficient reagent system, Ph3P/XCH2CH2X (X = Cl, Br, or I), was very effective for the deoxygenative halogenation (including fluorination) of alcohols (including tertiary alcohols) and aldehydes. The easily available 1,2-dihaloethanes were used as key reagents and halogen sources. The use of (EtO)3P instead of Ph3P could also realize deoxy-halogenation, allowing for a convenient purification process, as the byproduct (EtO)3Pa?O could be removed by aqueous washing. The mild reaction conditions, wide substrate scope, and wide availability of 1,2-dihaloethanes make this protocol attractive for the synthesis of halogenated compounds.
Deoxyfluorination of alcohols with aryl fluorosulfonates
Fei, Zhongbo,Hu, Jinbo,Li, Wei,Liu, Qinghe,Ni, Chuanfa,Wang, Xiu,Zhou, Min
supporting information, p. 8170 - 8173 (2021/08/23)
Aryl fluorosulfonates are developed as a deoxyfluorinating reagent in the transformation of primary and secondary alcohols into the corresponding alkyl fluorides. These reagents feature easy availability, low-cost, high stability and high efficiency. Diverse functionalities including aldehyde, ketone, ester, halogen, nitro, alkene, and alkyne are well tolerated under mild reaction conditions.
Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis
Webb, Eric W.,Park, John B.,Cole, Erin L.,Donnelly, David J.,Bonacorsi, Samuel J.,Ewing, William R.,Doyle, Abigail G.
supporting information, p. 9493 - 9500 (2020/05/18)
We report a redox-neutral method for nucleophilic fluorination of N-hydroxyphthalimide esters using an Ir photocatalyst under visible light irradiation. The method provides access to a broad range of aliphatic fluorides, including primary, secondary, and tertiary benzylic fluorides as well as unactivated tertiary fluorides, that are typically inaccessible by nucleophilic fluorination due to competing elimination. In addition, we show that the decarboxylative fluorination conditions are readily adapted to radiofluorination with [18F]KF. We propose that the reactions proceed by two electron transfers between the Ir catalyst and redox-active ester substrate to afford a carbocation intermediate that undergoes subsequent trapping by fluoride. Examples of trapping with O- and C-centered nucleophiles and deoxyfluorination via N-hydroxyphthalimidoyl oxalates are also presented, suggesting that this approach may offer a general blueprint for affecting redox-neutral SN1 substitutions under mild conditions.
A Series of Deoxyfluorination Reagents Featuring OCF2Functional Groups
Cao, Wei,Chen, Qing-Yun,Guo, Yong,Su, Zhaoben,Wu, Chengying,Zhao, Shiyu
supporting information, (2020/11/03)
Research on perfluoroalkyl ether carboxylic acids (PFECAs) as alternatives for perfluoroalkyl substances continues with the goal of protecting the environment. However, very little is known about the utilization of decomposition products of PFECAs. We report herein a new series of deoxyfluorination reagents featuring OCF2 functional groups derived from certain PFECAs. Alkyl fluorides were generated from various alcohols in ≤97% yield by these novel reagents. The mechanistic experiment verified in situ generation of carbonic difluoride (COF2).
Fluorination reagent and deoxygenation fluorination method
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Paragraph 0066-0116; 0127-0138; 0143-0144, (2020/12/30)
In order to overcome the problems of high cost and poor stability of the existing deoxidation fluorination reagent, the invention provides a fluorination reagent. The fluorination reagent comprises acation M and an anion, and the anion is selected from one or more of the following perfluoropolyether chain carboxylic acid anions: CF3 (OCF2) nCO2, and n is selected from 1-10. Meanwhile, the invention further discloses a deoxidation fluorination method. The fluorination reagent provided by the invention has the advantages that the materials are easy to obtain, the fluorination products can beobtained at higher yield for various alcohol substrates, and the universality for different alcohol substrates is better.
