360-11-2Relevant articles and documents
Alkali Metal Fluorides in Fluorinated Alcohols: Fundamental Properties and Applications to Electrochemical Fluorination
Shida, Naoki,Takenaka, Hiroaki,Gotou, Akihiro,Isogai, Tomohiro,Yamauchi, Akiyoshi,Kishikawa, Yosuke,Nagata, Yuuya,Tomita, Ikuyoshi,Fuchigami, Toshio,Inagi, Shinsuke
, p. 16128 - 16133 (2021/07/26)
Fundamental properties of alkali metal fluorides (MF, M = Cs, K) dissolved in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) or in 3,3,3-trifluoroethanol (TFE) are investigated, including solubility, conductivity, and viscosity. Solid-state structures of single crystals obtained from CsF/HFIP and CsF/TFE are described for the first time, giving insights into the multiple interactions between fluorinated alcohols and CsF. Applications in electrochemical fluorination reactions are successfully demonstrated.
Visible-light photoredox-catalyzed selective carboxylation of C(sp3)?F bonds with CO2
Bo, Zhi-Yu,Chen, Lin,Gao, Tian-Yu,Jing, Ke,Lan, Yu,Liu, Shi-Han,Luo, Shu-Ping,Yan, Si-Shun,Yu, Bo,Yu, Da-Gang
supporting information, p. 3099 - 3113 (2021/11/16)
It is highly attractive and challenging to utilize carbon dioxide (CO2), because of its inertness, as a nontoxic and sustainable C1 source in the synthesis of valuable compounds. Here, we report a novel selective carboxylation of C(sp3)?F bonds with CO2 via visible-light photoredox catalysis. A variety of mono-, di-, and trifluoroalkylarenes as well as α,α-difluorocarboxylic esters and amides undergo such reactions to give important aryl acetic acids and α-fluorocarboxylic acids, including several drugs and analogs, under mild conditions. Notably, mechanistic studies and DFT calculations demonstrate the dual role of CO2 as an electron carrier and electrophile during this transformation. The fluorinated substrates would undergo single-electron reduction by electron-rich CO2 radical anions, which are generated in situ from CO2 via sequential hydride-transfer reduction and hydrogen-atom-transfer processes. We anticipate our finding to be a starting point for more challenging CO2 utilization with inert substrates, including lignin and other biomass.
Pd-Catalyzed Transfer of Difluorocarbene for Three Component Cross-Coupling?
Xu, Zhi-Wei,Zhang, Wei,Lin, Jin-Hong,Jin, Chuan-Ming,Xiao, Ji-Chang
supporting information, p. 1647 - 1650 (2020/10/19)
Outstanding accomplishments have been achieved in the chemistry of difluorocarbene, but transition- metal-catalyzed transfer of difluorocarbene for coupling remains a challenging task. Herein, we describe a Pd-catalyzed coupling of difluorocarbene with two aryl carbon centers to give difluoromethylenation products, which cannot be obtained by any previous difluorocarbene-transformation method.
DIFLUOROMETHYL AND DIFLUOROMETHYLENE TRANSFER REAGENTS
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Paragraph 0022; 0096, (2020/01/22)
Disclosed herein are borazine, borate, and azaborinine compounds and compositions, methods of making said compounds and compositions, and methods of forming aromatic difluorocarbon compounds and difluorocarbon compounds.
Stoichiometric Studies on the Carbonylative Trifluoromethylation of Aryl Pd(II) Complexes using TMSCF3 as the Trifluoromethyl Source
Daasbjerg, Kim,Domino, Katrine,Johansen, Martin B.,Skrydstrup, Troels
supporting information, (2020/03/04)
We have performed a series of stoichiometric studies in order to identify viable steps for a hypothetical catalytic cycle for the palladium-mediated carbonylative coupling of an aryl bromide with TMSCF3. Our work revealed that benzoyl Pd(II) complexes bearing Xantphos or tBu3P as the phosphine ligands, which are generated from the corresponding PdII(Ph)Br complexes exposed to stoichiometric 13CO from 13COgen, were unable to undergo transmetalation and reductive elimination to trifluoroacetophenone. Instead, in the presence of base and additional CO, these organometallic complexes readily underwent reductive elimination to the acid fluoride. Attempts to determine whether the acid fluoride could represent an intermediate for acetophenone production were unrewarding. Only in the presence of a boronic ester did we observe some formation of the desired product, although the efficiency of transformation was still low. Finally, we investigated the reactivity of four phosphine-ligated PdII(Ph)CF3 complexes (Xantphos, DtBPF, tBu3P, and triphenylphosphine) with carbon monoxide. With the exception of the tBu3P-ligated complex, all other metal complexes led to the facile formation of trifluoroacetophenone. We also determined in the case of triphenylphosphine that CO insertion occurred into the Pd-Ar bond, as trapping of this complex with n-hexylamine led to the formation of n-hexylbenzamide.
The Difluoromethyl Group as a Masked Nucleophile: A Lewis Acid/Base Approach
Geri, Jacob B.,Wade Wolfe, Michael M.,Szymczak, Nathaniel K.
, p. 9404 - 9408 (2018/08/09)
The difluoromethyl group (R-CF2H) imparts desirable pharmacokinetic properties to drug molecules and is commonly targeted as a terminal functional group that is not amenable to further modification. Deprotonation of widely available Ar-CF2
Stoichiometric and Catalytic Aryl-Perfluoroalkyl Coupling at Tri-tert-butylphosphine Palladium(II) Complexes
Ferguson, Devin M.,Bour, James R.,Canty, Allan J.,Kampf, Jeff W.,Sanford, Melanie S.
supporting information, p. 11662 - 11665 (2017/09/07)
This Communication describes studies of Ph-RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (II complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes.
Activation of SF6 at Platinum Complexes: Formation of SF3 Derivatives and Their Application in Deoxyfluorination Reactions
Berg, Claudia,Braun, Thomas,Ahrens, Mike,Wittwer, Philipp,Herrmann, Roy
supporting information, p. 4300 - 4304 (2017/04/04)
The activation of SF6 at [Pt(PR3)2] R=Cy, iPr complexes in the presence of PR3 led selectively and in an unprecedented reaction route to the generation of the SF3 complexes trans-[Pt(F)(SF3)(PR3)2]. These can also be synthesized from SF4 and the SF2 derivative trans-[Pt(F)(SF2)(PCy3)2][BF4] was characterized by X-ray crystallography. trans-[Pt(F)(SF3)(PR3)2] complexes are useful tools for deoxyfluorination reactions and novel fluorido complexes bearing a SOF ligand are formed. Based on these studies a process for the deoxyfluorination of ketones was developed with SF6 as fluorinating agent.
FLUORINATING AGENT
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Paragraph 0092; 0099, (2016/12/01)
An object of the present invention is to provide a novel substance that has a high reactivity as a fluorinating agent, is effectively used in various fluorination reactions, and is safely handled even in air. As the solution for achieving this object, the present invention provides a complex obtained by reacting bromine trifluoride with at least one metal halide selected from the group consisting of halogenated metals and halogenated hydrogen metals in a nonpolar solvent. This complex serves as a fluorinating agent that provides excellent fluorination performance and that is stable in air.
(Re)Investigation of the reactivity of uranium hexafluoride toward several organic functions at room temperature
Roy, Olivier,Marquet, Bernard,Alric, Jean-Paul,Jourdan, Alex,Morel, Bertrand,Langlois, Bernard R.,Billard, Thierry
, p. 74 - 78 (2015/03/04)
The annual worldwide production of UF6 is very large and this compound is not used. Consequently, it could be interesting to find some applications as organic reagent. UF6 could be considered as an oxidizer of various functions. However, it seems also present some possibilities as a fluorinating reagent in mild conditions.
