10304-79-7Relevant academic research and scientific papers
Photoredox Polyfluoroarylation of Alkyl Halides via Halogen Atom Transfer
Blackburn, Bryan G.,Cooke, Maria Victoria,Laulhé, Sébastien,Niu, Ben,Sachidanandan, Krishnakumar
supporting information, p. 916 - 920 (2022/02/07)
Polyfluoroarene moieties are of interest in medicinal chemistry, agrochemicals, and material sciences. Herein, we present the first polyfluoroarylation of unactivated alkyl halides via a halogen atom transfer process. This method converts primary, secondary, and tertiary alkyl halides into the respective polyfluoroaryl compounds in good yields in the presence of amide, carbamate, ester, aromatic, and sulfonamide moieties, including derivatives of complex bioactive molecules. Mechanistic work revealed that this transformation proceeds through an alkyl radical generated after the halogen atom transfer.
Photocatalytic Decarboxylative Coupling of Aliphatic N-hydroxyphthalimide Esters with Polyfluoroaryl Nucleophiles
Hu, Xile,Lavrencic, Lara,Mao, Runze,Yi, Xiangli
supporting information, p. 23557 - 23563 (2021/09/30)
Polyfluoroarenes are an important class of compounds in medical and material chemistry. The synthesis of alkylated polyfluoroarenes remains challenging. Here we describe a decarboxylative coupling reaction of N-hydroxyphthalimide esters of aliphatic carboxylic acids with polyfluoroaryl zinc reagents (Zn-ArF) via synergetic photoredox and copper catalysis. This method readily converts primary and secondary alkyl carboxylic acids into the corresponding polyfluoroaryl compounds, which could have a wide range of F-content (2F-5F) and variable F-substitution patterns on the aryl groups. Broad scope and good functional group compatibility were achieved, including on substrates derived from natural products and pharmaceuticals. Mechanistic study revealed that a [Cu-(ArF)2] species could be responsible for the transfer of polyfluoroaryl groups to the alkyl radicals.
Interactions of C?F Bonds with Hydridoboranes: Reduction, Borylation and Friedel–Crafts Alkylation
Bamford, Karlee L.,Chitnis, Saurabh S.,Qu, Zheng-wang,Stephan, Douglas W.
supporting information, p. 16014 - 16018 (2018/10/15)
The stoichiometric reactions of the alkylfluorides 1-fluoroadamantane (Ad-F), fluorocyclohexane (Cy-F), 1-fluoropentane (Pent-F) and benzyl fluorides with secondary boranes pinacolborane (HBpin), catecholborane (HBcat), 9-borabicyclo(3.3.1)nonane (9-BBN)
“π-Hole?π” Interaction Promoted Photocatalytic Hydrodefluorination via Inner-Sphere Electron Transfer
Lu, Jingzhi,Khetrapal, Navneet S.,Johnson, Jacob A.,Zeng, Xiao Cheng,Zhang, Jian
supporting information, p. 15805 - 15808 (2016/12/23)
We describe a metal-free, photocatalytic hydrodefluorination (HDF) of polyfluoroarenes (FA) using pyrene-based photocatalysts (Py). The weak “π-hole?π” interaction between Py and FA promotes the electron transfer against unfavorable energetics (ΔGET up to 0.63 eV) and initiates the subsequent HDF. The steric hindrance of Py and FA largely dictates the HDF reaction rate, pointing to an inner-sphere electron transfer pathway. This work highlights the importance of the size and shape of the photocatalyst and the substrate in controlling the electron transfer mechanism and rates as well as the overall photocatalytic processes.
Photosubstitution reactions on aromatic and heteroaromatic rings evidence for addition and substitution mechanism
Sket, Boris,Zupan, Marko,Zupancic, Natasa,Pahor, Barbara
, p. 5029 - 5042 (2007/10/02)
Irradiation of a cyclohexane solution of hexafluorobenzene in the presence of benzophenone resulted in both, substitution and addition products. Similar photoreaction has been observed by irradiation of hexafluorobenzene in some alcohols in the presence of benzophenone. The reaction of pentafluorobenzene with methanol or cyclohexane resulted in the substitution of a 2-or 4-fluoro atom, while the reaction of pentafluoroanisole resulted in the formation of o-, m- and p-isomers. Irradiation of a cyclohexane solution or of an alcohol solution of octafluoronaphthalene yielded 1- and 2-substituted products. On the other hand, the photosubstitution of fluorine atom in pentafluoropyridine took place exclusively at the position four, thus forming 4-cyclohexyl or 4-(1-hydroxyalkyl) substituted products.
