379-50-0Relevant articles and documents
Metal-free hydrogen evolution cross-coupling enabled by synergistic photoredox and polarity reversal catalysis
Cao, Jilei,Lu, Kanghui,Ma, Lishuang,Yang, Xiaona,Zhou, Rong
supporting information, p. 8988 - 8994 (2021/11/23)
A synergistic combination of photoredox and polarity reversal catalysis enabled a hydrogen evolution cross-coupling of silanes with H2O, alcohols, phenols, and silanols, which afforded the corresponding silanols, monosilyl ethers, and disilyl ethers, respectively, in moderate to excellent yields. The dehydrogenative cross-coupling of Si-H and O-H proceeded smoothly with broad substrate scope and good functional group compatibility in the presence of only an organophotocatalyst 4-CzIPN and a thiol HAT catalyst, without the requirement of any metals, external oxidants and proton reductants, which is distinct from the previously reported photocatalytic hydrogen evolution cross-coupling reactions where a proton reduction cocatalyst such as a cobalt complex is generally required. Mechanistically, a silyl cation intermediate is generated to facilitate the cross-coupling reaction, which therefore represents an unprecedented approach for the generation of silyl cationviavisible-light photoredox catalysis.
PROCESS FOR PRODUCING SULFONIC ACID GROUP-CONTAINING MONOMER
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, (2021/01/22)
The present disclosure is directed to provide a process capable of producing a sulfonic acid group-containing monomer in a good yield, which can be used as a raw material of fluorine-based polymer electrolytes, such as membranes for fuel cells, catalyst binder polymers for fuel cells, and membranes for chlor-alkali electrolysis. A process for producing a sulfonic acid group-containing monomer represented by the general formula (3) includes the step of mixing and stirring a cyclic compound represented by the general formula (1) and a silanol compound represented by the general formula (2).
C?H and C?F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO-1234yf
Talavera, Maria,von Hahmann, Cortney N.,Müller, Robert,Ahrens, Mike,Kaupp, Martin,Braun, Thomas
supporting information, p. 10688 - 10692 (2019/07/10)
The reaction of [Rh(H)(PEt3)3] (1) with the refrigerant HFO-1234yf (2,3,3,3-tetrafluoropropene) affords an efficient route to obtain [Rh(F)(PEt3)3] (3) by C?F bond activation. Catalytic hydrodefluorinations were achieved in the presence of the silane HSiPh3. In the presence of a fluorosilane, 3 provides a C?H bond activation followed by a 1,2-fluorine shift to produce [Rh{(E)-C(CF3)=CHF}(PEt3)3] (4). Similar rearrangements of HFO-1234yf were observed at [Rh(E)(PEt3)3] [E=Bpin (6), C7D7 (8), Me (9)]. The ability to favor C?H bond activation using 3 and fluorosilane is also demonstrated with 3,3,3-trifluoropropene. Studies are supported by DFT calculations.
Facile synthesis of cyclic fluorosiloxanes
Oguri, Naoki,Takeda, Nobuhiro,Unno, Masafumi
supporting information, p. 1506 - 1508 (2015/11/24)
Novel 1,3,5,7-tetrafluorocyclotetrasiloxanes were synthesized from cyclotetrasiloxanetetraol by a facile synthetic method. By adjusting the amount of the fluorinating reagent, synthesis of a single isomer of 1,3,5,7-tetrafluorocyclotetrasiloxanes as well as the preparation of all four isomers were accomplished. The products are expected to serve as potential precursors to not only well-defined silsesquioxanes but also asymmetric cyclic siloxanes.
[B(C6F5)4]: An air stable, lewis acidic stibonium salt that activates strong element-fluorine bonds
Pan, Baofei,Gabba?, Fran?ois P.
supporting information, p. 9564 - 9567 (2014/07/22)
As part of our ongoing interest in main group Lewis acids for fluoride anion complexation and element-fluorine bond activation, we have synthesized the stibonium borate salt [Sb(C6F5)4][B(C 6F5)4] (3). The perfluorinated stibonium cation [Sb(C6F5)4]+ present in this salt is a potent Lewis acid which abstracts a fluoride anion from [SbF 6]- and [BF(C6F5)3] - indicating that it is a stronger Lewis acid than SbF5 and B(C6F5)3. The unusual Lewis acidic properties of 3 are further reflected by its ability to polymerize THF or to promote the hydrodefluorination of fluoroalkanes in the presence of Et 3SiH. While highly reactive in solution, 3 is a perfectly air stable salt, making it a convenient Lewis acidic reagent.
Preparation of (Z)-1-fluoro-1-alkenyl carboxylates, carbonates and carbamates through chromium mediated transformation of dibromofluoromethylcarbinyl esters and the reactivity as double acyl group donors
Saito, Akio,Tojo, Manabu,Yanai, Hikaru,Wada, Fukiko,Nakagawa, Muga,Okada, Midori,Sato, Azusa,Okatani, Rieko,Taguchi, Takeo
experimental part, p. 38 - 51 (2012/02/04)
CrCl2/Mn-mediated transformation of various dibromofluoromethylcarbinyl esters including carboxylates, carbonates and carbamates provided 1-fluoro-1-alkenyl esters via [2,3]-sigmatropic rearrangement of ester group. Reaction proceeded by using CrCl2/Mn system under mild conditions (in THF at room temperature) to give 1-fluoro-1-alkenyl esters in good yield with an excellent Z selective manner. 1-Fluoro-1-alkenyl ester thus obtained acts as a double acyl donor in the reaction with necleophiles such as amine, thiol, alcohol as well as bifunctional necleophiles such as ethylene diamine derivative.
Meerwein's reagent mediated, significantly enhanced nucleophilic fluorination on alkoxysilanes
Jorapur, Yogesh R.,Shimada, Toyoshi
scheme or table, p. 1064 - 1068 (2012/06/17)
We developed a new facile method to fluorosilanes from alkoxysilanes using Meerwein's reagent. Our protocol afforded fluorosilanes in excellent yields in various organic solvents including acetonitrile under mild reaction conditions at room temperature. We also proposed a reaction mechanism with the probable silyloxonium intermediates. Georg Thieme Verlag Stuttgart · New York.
Synthesis, structure and reactivity of iridium hydrido fluorido complexes
Klaering, Paul,Jungton, Ann-Katrin,Braun, Thomas,Mueller, Carsten
experimental part, p. 1430 - 1436 (2012/06/15)
The oxidative addition of HF at trans-[Ir(ArF) (η2-C2H4)(PiPr3)2] (1a: ArF = 4-C5NF4; 1b: ArF = 2-C6H3F2) affords the fluorido complexes trans-[Ir(ArF)(F)(H)(PiPr3)2] (2a: Ar F = 4-C5NF4; 2b: ArF = 2-C 6H3F2). The hydrido fluorido complex 2a is also accessible by means of the reaction of the hydroxido complex trans-[Ir(4-C 5NF4)(H)(OH)(PiPr3)2] (3a) with Et3N·3HF. Both compounds 2a and 2b react with CO to give the carbonyl complexes trans-[Ir(4-C5NF4)(F)(H)(CO)(PiPr 3)2] (4a: ArF = 4-C5NF4; 4b: ArF = 2-C6H3F2). In the presence of traces of water, a slow reaction of 2a with CO2 yields the hydrogencarbonato complex trans-[Ir(4-C5NF4)(H)( 2-(O,O)-O2COH)(PiPr3)2] (5a). Upon using 2a or 2b as fluorinating agent, Ph3SiH could be converted into Ph3SiF and CH3C(O)Cl into CH3C(O)F. The oxidative addition of HF at trans-[Ir(4-C5NF4) (I·2-C2H4)(PiPr3) 2] affords the fluorido complex trans-[Ir(4-C5NF 4)(F)(H)(PiPr3)2], which exhibits a square-pyramidal configuration. The latter reacts with acetyl chloride to yield acetyl fluoride and trans-[Ir(4-C5NF4)(Cl)(H)(PiPr 3)2].
Equilibrium shift in the rhodium-catalyzed acyl transfer reactions
Arisawa, Mieko,Igarashi, Yui,Kobayashi, Haruki,Yamada, Toru,Bando, Kentaro,Ichikawa, Takuya,Yamaguchi, Masahiko
supporting information; experimental part, p. 7846 - 7859 (2011/10/12)
Rhodium/phosphine complexes catalyze equilibrium acyl transfer reactions between acid fluorides, aryl esters, acylphosphine sulfides, and thioesters. The use of appropriate co-substrates to accept heteroatom groups shifted the equilibrium to desired products. Acylphosphine sulfides and aryl esters were converted to acid fluorides using benzoylpentafluorobenzene as the fluoride donor, and the fluorination reaction of thioesters employed (4-tolylthio) pentafluorobenzene. Acid fluorides were converted into acylphosphine sulfides and thioesters using diphosphine disulfides and disulfides/triphenylphosphine, respectively. Aryl esters were obtained from acid fluorides and phenols in the presence of triphenylsilane. Aryl esters, acylphosphine sulfides, and thioesters were also interconverted in the presence of rhodium complexes. These rhodium-catalyzed acyl transfer reactions proceeded under neutral conditions without using acid or base. The involvement of acyl rhodium intermediates in these reactions was suggested by the carbothiolation reaction of thioesters and alkynes.
Sequential C-F activation and borylation of fluoropyridines via intermediate Rh(i) fluoropyridyl complexes: A multinuclear NMR investigation
Lindup, Richard J.,Marder, Todd B.,Perutz, Robin N.,Whitwood, Adrian C.
, p. 3664 - 3666 (2008/03/14)
The C-F bond activation of fluoropyridines by [Rh(SiPh3) (PMe3)3] afforded Rh(i) fluoropyridyl complexes of the type [Rh(ArF)(PMe3)3] with concomitant formation of fluorotriphenylsilane; subsequent treatment with bis-catecholatodiboron yielded fac-[Rh(Bcat)3(PMe3) 3] and the free fluoropyridyl boronate esters (ArFBcat). The Royal Society of Chemistry.
