104315-86-8Relevant articles and documents
Copper-Catalyzed Trifluoromethylation of Alkyl Bromides
Kornfilt, David J.P.,Macmillan, David W.C.
, p. 6853 - 6858 (2019)
Copper oxidative addition into organohalides is a challenging two-electron process. In contrast, formal oxidative addition of copper to C sp2 carbon-bromine bonds can be accomplished by employing latent silyl radicals under photoredox conditions. This novel paradigm for copper oxidative addition has now been applied to a Cu-catalyzed cross-coupling of C sp3-bromides. Specifically, a copper/photoredox dual catalytic system for the coupling of alkyl bromides with trifluoromethyl groups is presented. This operationally simple and robust protocol successfully converts a variety of alkyl, allyl, benzyl, and heterobenzyl bromides into the corresponding alkyl trifluoromethanes.
The first Cu(I)-mediated nucleophilic trifluoromethylation reactions using (trifluoromethyl)trimethylsilane in ionic liquids
Kim, Jinwi,Shreeve, Jean'ne M.
, p. 2728 - 2734 (2004)
The new ionic liquids (5a-8a) were used as reaction media for nucleophilic trifluoromethylation reactions of trifluoromethyl(trimethyl)silane with (1) aryl, allyl, benzyl, and alkyl halides in Cu(I)-mediated C-C bond formation reactions, and (2) carbonyl functionalities catalyzed with Ph3P or CsF. In addition, conversion of benzyl bromide as a model compound to benzyl fluoride was examined in 6a using CsF as the fluorinating reagent. The morpholiniumbased ionic liquid (6a) stood out as an efficient solvent system comparable to organic solvents and superior to the other new ionic liquids prepared in this work as well as to [bmim]+[PF6]-. Neat reactions of N-methyloxazolidine (1), Af-methylmorpholine (2), A'-methylimidazole (3) or TV-methyltriazole (4) with 2-(2-ethoxyethoxy)ethyl bromide (BrCH2CH2OCH2CH2OCH 2CH3, 9) or 2-bromoethyl methyl ether (BrCH 2CH2OCH3,10) at 75 or 105 °C gave the A'-(2-ethoxyethoxy)ethyl- or N-methoxyethyl-substituted oxazolidinium, morpholinium, imidazolium and triazolium quaternary bromides (1a-4a, 1b-4b) which were metathesized with LiN(SO2CF3)2 to form the respective roomtemperature liquid bis(trifluoromethanesulfonyl)amides 5a-8a and 5b-8b in high yields with transition or melting points 310 °C as determined by thermogravimetric analyses (TGA). Densities range between 1.29 and 1.53 g cm-3 at 25 °C.
Nickel-catalyzed carbonylation of secondary trifluoromethylated, difluoromethylated, and nonfluorinated aliphatic electrophiles with arylboronic acids under 1 atm of co
Cheng, Ran,Zhao, Hai-Yang,Zhang, Shu,Zhang, Xingang
, p. 36 - 42 (2020)
The nickel-catalyzed carbonylation of aliphatic electrophiles with the most straightforward CO remains challenging. Here, we describe an example of the nickel-catalyzed carbonylation of secondary alkyl halides with arylboronic acids under 1 atm of CO. The reaction exhibits high functional group tolerance and a broad substrate scope, including trifluoromethylated, difluoromethylated, and difluoroacetylated secondary alkyl iodides and secondary benzyl bromides, providing a general and cost-efficient method to access alkyl ketones, especially α-trifluoromethylated alkyl ketones that are of great interest in medicinal chemistry. Preliminary mechanistic studies reveal that a bimetallic oxidative addition is likely involved in the reaction.
Method for preparing fluoroalkane substituted compound by reducing halogenated fluoroalkane and olefin through metal elementary substance
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Paragraph 0061-0069; 0275-0283, (2021/07/17)
The invention discloses a method for preparing a fluoroalkane substituted compound, which comprises the steps of taking a compound containing carbon-carbon double bonds and halogenated fluoroalkane as raw materials, taking a metal elementary substance as a reducing agent, taking a substance containing active protons as a hydrogen source, and carrying out an addition reaction to prepare a compound which is simultaneously substituted by hydrogen and fluoroalkyl, thereby obtaining the fluoroalkane substituted compound. According to the method, the metal elementary substance is used as the reducing agent for the first time, the compound containing active hydrogen is used as the hydrogen source, one hydrogen atom and one fluoroalkyl group are introduced to the two ends of olefin respectively, only one-step reaction is needed, the reaction process conditions are mild, the reaction raw materials are cheap and easy to obtain, the cost is low, and all reaction reagents are green and environmentally friendly; and the reaction substrate has strong applicability, can participate in the reaction as long as carbon-carbon double bonds exist in the structure, and is not influenced by the types of substituent groups on carbon atoms of the double bonds, and the yield of the product is good.
Cobalt-Catalyzed Radical Hydrotrifluoroethylation of Styrenes with Trifluoroethyl Iodide
He, Bin,Pan, Qijun,Guo, Yong,Chen, Qing-Yun,Liu, Chao
supporting information, p. 6552 - 6556 (2020/09/02)
The cobalt-catalyzed radical trifluoroethylation of styrenes with CF3CH2I under mild conditions is described. By controlling the reaction conditions, we realized both radical trifluoroethylation self-coupling and hydrotrifluoroethylation of styrenes. The
Radical-Mediated Strategies for the Functionalization of Alkenes with Diazo Compounds
Su, Yong-Liang,Liu, Geng-Xin,Liu, Jun-Wen,Tram, Linh,Qiu, Huang,Doyle, Michael P.
supporting information, p. 13846 - 13855 (2020/09/21)
One of the most common reactions of diazo compounds with alkenes is cyclopropanation, which occurs through metal carbene or free carbene intermediates. Alternative functionalization of alkenes with diazo compounds is limited, and a methodology for the addition of the elements of Z-CHR2 (with Z = H or heteroatom, and CHR2 originates from N2 CR2) across a carbon-carbon double bond has not been reported. Here we report a novel reaction of diazo compounds utilizing a radical-mediated addition strategy to achieve difunctionalization of diverse alkenes. Diazo compounds are transformed to carbon radicals with a photocatalyst or an iron catalyst through PCET processes. The carbon radical selectively adds to diverse alkenes, delivering new carbon radical species, and then forms products through hydroalkylation by thiol-assisted hydrogen atom transfer (HAT), or forms azidoalkylation products through an iron catalytic cycle. These two processes are highly complementary, proceed under mild reaction conditions, and show high functional group tolerance. Furthermore, both transformations are successfully performed on a gram-scale, and diverse γ-amino esters, γ-amino alcohols, and complex spirolactams are easily prepared with commercially available reagents. Mechanistic studies reveal the plausible pathways that link the two processes and explain the unique advantages of each.
Copper-Catalyzed Photoinduced Enantioselective Dual Carbofunctionalization of Alkenes
Chen, Bin,Li, Chen,Sun, Youwen,Xu, Meichen,Zhang, Dayong,Zhang, Guozhu,Zhang, Yajing
supporting information, (2020/02/28)
A photoinduced, copper-catalyzed, highly enantioselective dual alkylation/arylation and alkynylation of alkene is reported. A single chiral copper(I) complex serves to enable photoredox catalysis and induce enantioselectivity during the reaction. This reaction couples three different components under mild reaction conditions, exhibits a broad substrate scope, and provides facile access to chiral propargylic systems, including those featuring valuable fluorinated substituents.
Reductive C-C Coupling by Desulfurizing Gold-Catalyzed Photoreactions
Zhang, Lumin,Si, Xiaojia,Yang, Yangyang,Witzel, Sina,Sekine, Kohei,Rudolph, Matthias,Rominger, Frank,Hashmi, A. Stephen K.
, p. 6118 - 6123 (2019/07/03)
[Au2(μ-dppm)2]Cl2-mediated photocatalysis reactions are usually initiated by ultraviolet A (UVA) light; herein, an unreported system using blue light-emitting diodes (LEDs) as excitation light source was found. The red shift of the absorption wavelength originates from the combination of [Au2(μ-dppm)2]Cl2 and ligand (Ph3P or mercaptan). On the basis of this finding, a gold-catalyzed reductive desulfurizing C-C coupling of electrophilic radicals and styrenes mediated by blue LEDs is presented, a coupling which cannot be efficiently accessed by previously reported methods. This mild and highly efficient C-C bond formation strategy uses mercaptans both as electron-deficient alkyl radical precursor as well as the hydrogen source. Two examples of amino acids have also been modified by using this strategy. Moreover, this methodology could be applied in polymer synthesis. Gram-scale synthesis and mechanistic insights into this transformation are also presented.
Photoredox-Assisted Reductive Cross-Coupling: Mechanistic Insight into Catalytic Aryl-Alkyl Cross-Couplings
Paul, Avishek,Smith, Mark D.,Vannucci, Aaron K.
, p. 1996 - 2003 (2017/02/26)
Here, we describe a photoredox-assisted catalytic system for the direct reductive coupling of two carbon electrophiles. Recent advances have shown that nickel catalysts are active toward the coupling of sp3-carbon electrophiles and that well-controlled, light-driven coupling systems are possible. Our system, composed of a nickel catalyst, an iridium photosensitizer, and an amine electron donor, is capable of coupling halocarbons with high yields. Spectroscopic studies support a mechanism where under visible light irradiation the Ir photosensitizer in conjunction with triethanolamine are capable of reducing a nickel catalyst and activating the catalyst toward cross-coupling of carbon electrophiles. The synthetic methodology developed here operates at low 1 mol % catalyst and photosensitizer loadings. The catalytic system also operates without reaction additives such as inorganic salts or bases. A general and effective sp2-sp3 cross-coupling scheme has been achieved that exhibits tolerance to a wide array of functional groups.
Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in Batch and Flow
Straathof, Natan J. W.,Cramer, Sten E.,Hessel, Volker,No?l, Timothy
supporting information, p. 15549 - 15553 (2016/12/09)
Styrenes represent a challenging class of substrates for current radical trifluoromethylation and hydrotrifluoromethylation methods due to a myriad of potential side reactions. Herein, we describe the development of mild, selective and broadly applicable photocatalytic trifluoromethylation and hydrotrifluoromethylation protocols for these challenging substrates. The methods use fac-Ir(ppy)3, visible light and inexpensive CF3I and can be applied to a diverse set of vinylarene substrates. The use of continuous-flow photochemical reaction conditions allowed to reduce the reaction time and increase the reaction selectivity.
