- Chiral trifluoromethylphosphines: A new stereoselective synthesis of Josiphos-type ligands containing two stereogenic phosphorus atoms
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Intramolecular nucleophilic substitution of a trifluoromethyl group to form a 1,2-diphosphole derivative followed by the sequential addition of an alkylating agent and a carbanion are the key steps in the stereoselective synthesis of novel ferrocenyl diph
- Buergler, Jonas F.,Togni, Antonio
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- NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a simple method for producing trifluoromethyltriol borate potassium from trifluoromethane. SOLUTION: There is provided a method for producing a compound represented by the formula [7], comprising: reacting a monohydroperfluoroalkane with a base and trialkyl borate in an organic solvent; and then reacting the reaction solution with triol. [In the formula, RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R6 is H or a C1-2 linear alkyl group, or the like; M may be a metal or the like belonging to Group I, Group II, Group III, Group IV, Group V, Group VI, Group VII, Group VIII, Group IX, Group X, Group XI, Group XII, and Group XIII in the periodic table of elements, and they may be a single substance or a mixture of a plurality of substances and y corresponds to the oxidation number of the substance represented by M.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0119-0120
(2021/04/09)
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- NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for producing an aromatic perfluoroalkyl compound using silylated trifluoromethyl carbinol. SOLUTION: There is provided a method for producing an aromatic perfluoroalkyl compound represented by the general formula [10], in which a compound represented by the formula [9] and a compound represented by the formula [1] are reacted in an organic solvent in the presence of a copper catalyst, a nitrogen ligand and a metal fluoride. R7-X...[9], RF-R7...[10] [In the formula, R7 is an aryl group or the like which may have a substituent; X is F, Cl, Br or I; RF is an alkyl group such as a linear chain of C1-2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are each independently H or a C1-2 linear alkyl group, or the like; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are each independently H or a C1-2 linear alkyl group, or the like.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
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Paragraph 0119-0120
(2021/04/09)
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- NOVEL METHOD FOR PRODUCING PERFLUOROALKYLATING AGENTS USING MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR PRODUCING AROMATIC PERFLUOROALKYL COMPOUNDS USING THE SAME
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To provide a simple method for producing silylated trifluoromethylcarbinol from trifluoromethane.SOLUTION: There is provided a method for producing a compound represented by the formula [1], in which the compound is obtained by reacting a monohydroperfluoroalkane, a carbonyl compound, and NaH in an organic solvent and then reacting the reaction solution with a silylating agent. [In the formula, RF is an alkyl group such as a linear chain of C1 to 2, and a perfluoroalkyl group in which all H on C is substituted with F; R1 and R2 are independently alkyl groups such as a linear chain of H or C1 to 2, or the like respectively; R1 and R2 may be integrated to form a ring; and R3, R4 and R5 are independently H or C1 to 2 linear alkyl groups, or the like respectively.]SELECTED DRAWING: None
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Paragraph 0119-0120
(2021/04/02)
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- Formation of a hydride containing amido-zincate using pinacolborane
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Amido-zincates containing hydrides are underexplored yet potentially useful complexes. Attempts to access this type of zincate through combining amido-organo zincates and pinacolborane (HBPin)viaZn-C/H-BPin exchange led instead to preferential formation of amide-BPin and/or [amide-BPin(Y)]?(Y = Ph, amide, H), when the amide is hexamethyldisilazide or 2,2,6,6-tetramethylpiperidide and the hydrocarbyl group was phenyl or ethyl. In contrast, the use of a dipyridylamide (dpa) based arylzinc complex led to Zn-C/H-BPin metathesis being the major outcome. Independent synthesis and full characterisation of two LnLi[(dpa)ZnPh2] (L = THF,n= 3; L = PMDETA,n= 1) complexes,1and3, respectively, enabled reactivity studies that demonstrated that these species display zincate type reactivity (by comparison to the lower reactivity of the neutral complex (Me-dpa)ZnPh2,4, Me-dpa = 2,2′-dipyridyl-N-methylamine). This included1performing the rapid deprotonation of 4-ethynyltoluene and also phenyl transfer to α,α,α-trifluoroacetophenone in contrast to neutral complex4. Complex1reacted with one equivalent of HBPin to give predominantly PhBPin (ca.90%) and a lithium amidophenylzincate containing a hydride unit, complex7-A, as the major zinc containing product. Complex7-Atransfers hydride to an electrophile preferentially over phenyl, indicating it reacts as a hydridozincate. Attempts to react1with >1 equivalent of HBPin or with catecholborane led to more complex outcomes, which included significant borane and dpaZn substituent scrambling, two examples of which were crystallographically characterised. While this work provides proof of principle for Zn-C/H-BPin exchange as a route to form an amido-zincate containing a hydride, amido-organozincates that undergo more selective Zn-C/H-BPin exchange still are required.
- Ingleson, Michael J.,Nichol, Gary S.,Uzelac, Marina,Yuan, Kang
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supporting information
p. 14018 - 14026
(2021/10/19)
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- Gas/Liquid-Phase Micro-Flow Trifluoromethylation using Fluoroform: Trifluoromethylation of Aldehydes, Ketones, Chalcones, and N-Sulfinylimines
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A micro-flow nucleophilic trifluoromethylation of carbonyl compounds using gaseous fluoroform was developed. This method also allows the first micro-flow transformation of N-sulfinylimines into trifluoromethyl amines with excellent diastereoselectivity. To demonstrate the synthetic utility of this micro-flow synthesis, the formal micro-flow synthesis of Efavirenz is described.
- Hirano, Kazuki,Gondo, Satoshi,Punna, Nagender,Tokunaga, Etsuko,Shibata, Norio
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p. 406 - 410
(2019/02/13)
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- PREPARATION PROCESS OF PERFLUOROALKYL COMPOUND WITH MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL
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A simple production process is provided of a perfluoroalkyl compound that uses monohydroperfluoroalkane as a starting material, the perfluoroalkyl compound being an important intermediate of organic electronic materials, medicine, agricultural chemicals,
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Paragraph 0072-0076
(2019/06/17)
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- METHOD FOR PRODUCING TRIFLUOROMETHYL GROUP-CONTAINING ALCOHOLS
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PROBLEM TO BE SOLVED: To provide a method for producing trifluoromethyl group-containing alcohols useful as synthetic intermediates for medicines and agrochemicals. SOLUTION: This invention relates to a method for producing trifluoromethyl group-containing alcohols expressed by a formula (2), comprising: making carbonyl compounds expressed by a formula (1) react with trifluoromethane in an organic solvent in the presence of polyvalent ethers and potassium tert-butoxide, or kalium hexamethyldisilazide. (R1 and R2 are each independently a phenyl group etc.; R2 may combine with R1, to form a ring, and both R1 and R2 are not hydrogen atoms). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0075-0078
(2018/04/10)
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- NEW MANUFACTURING METHOD OF PERFLUORO ALKYLATING AGENT WHICH USED MONOHYDROPERFLUOROALKANE AS STARTING MATERIAL, AND METHOD FOR MANUFACTURING AROMATIC PERFLUORO ALKYL COMPOUND USING THE SAME
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PROBLEM TO BE SOLVED: To provide a method for manufacturing silanized trifluoromethyl carbinol, potassium trifluoromethyl triol borate and an aromatic trifluoromethyl compound from trifluoromethane. SOLUTION: There are provided a method for manufacturing silanized trifluoromethyl carbinol in which trifluoromethyl carbinol obtained by reacting trifluoromethane with a carbonyl compound in the presence of a base is reacted with silanizing agent; or a method for manufacturing potassium trifluoromethyl triol borate in which potassium trifluoromethyl trimethoxy borate obtained by reacting trifluoromethane with trimethoxy borane in the presence of a base is reacted with a triol; and a method for manufacturing an aromatic trifluoromethyl compound obtained by making an aromatic iodide act on silanized trifluoromethyl carbinol or potassium trifluoromethyl triol borate in the presence of catalytic amount of copper (I) iodide and 9,10-phenanthroline. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
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Paragraph 0119; 0120
(2018/12/14)
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- Introducing Glycerol as a Sustainable Solvent to Organolithium Chemistry: Ultrafast Chemoselective Addition of Aryllithium Reagents to Nitriles under Air and at Ambient Temperature
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Edging closer towards developing air and moisture compatible polar organometallic chemistry, the chemoselective and ultrafast addition of a range of aryllithium reagents to nitriles has been accomplished by using glycerol as a solvent, at ambient temperature in the presence of air, establishing a novel sustainable access to aromatic ketones. Addition reactions occur heterogeneously (“on glycerol conditions”), where the lack of solubility of the nitriles in glycerol and the ability of the latter to form strong intermolecular hydrogen bonds seem key to favouring nucleophilic addition over competitive hydrolysis. Remarkably, PhLi exhibits a greater resistance to hydrolysis working “on glycerol” conditions than “on water”. Introducing glycerol as a new solvent in organolithium chemistry unlocks a myriad of opportunities for developing more sustainable, air and moisture tolerant main-group-metal-mediated organic synthesis.
- Rodríguez-álvarez, María J.,García-álvarez, Joaquín,Uzelac, Marina,Fairley, Michael,O'Hara, Charles T.,Hevia, Eva
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p. 1720 - 1725
(2018/01/27)
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- Recyclable Trifluoromethylation Reagents from Fluoroform
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We present a strategy to rationally prepare CF3- transfer reagents at ambient temperature from HCF3. We demonstrate that a highly reactive CF3- adduct can be synthesized from alkali metal hydride, HCF3, and borazine Lewis acids in quantitative yield at room temperature. These nucleophilic reagents transfer CF3- to substrates without additional chemical activation, and after CF3 transfer, the free borazine is quantitatively regenerated. These features enable syntheses of popular nucleophilic, radical, and electrophilic trifluoromethylation reagents with complete recycling of the borazine Lewis acid.
- Geri, Jacob B.,Szymczak, Nathaniel K.
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supporting information
p. 9811 - 9814
(2017/08/03)
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- METHOD FOR PRODUCING TRIFLUOROMETHYL GROUP-CONTAINING ALCOHOLS
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PROBLEM TO BE SOLVED: To provide a method for producing CF3 group-containing alcohols useful as production intermediates for medicines and agrochemicals. SOLUTION: The method for producing CF3 group-containing alcohols represented by formula (2) comprises
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Paragraph 0029-0031
(2017/02/02)
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- Flow trifluoromethylation of carbonyl compounds by Ruppert-Prakash reagent and its application for pharmaceuticals, efavirenz and HSD-016
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The Ruppert-Prakash reagent is the most powerful and well-documented reagent for trifluoromethylation. Despite its versatility, no general method exists for its use in a flow system. Here we report the first flow trifluoromethylation of carbonyl compounds
- Okusu, Satoshi,Hirano, Kazuki,Yasuda, Yoshimasa,Tokunaga, Etsuko,Shibata, Norio
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p. 82716 - 82720
(2016/11/11)
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- A method of manufacturing a trifluoromethyl group-containing compound
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PROBLEM TO BE SOLVED: To provide a method for producing a trifluoromethyl group-containing compound useful as a synthetic intermediate for a pharmaceutical or an agricultural chemical product.SOLUTION: There is provided a method for producing a trifluoromethyl group-containing compound represented by the following general formula (2) which is obtained by reacting a carbonyl compound having a specific structure with trifluoromethane and an organic base in an organic solvent (wherein, Rrepresents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 10 carbon atoms, a phenyl group, a substituted phenyl group, a naphthyl group, a substituted naphthyl group, an ethenyl group, a 2-phenylethenyl group, a 9-anthryl group or a hetero ring; Rrepresents a hydrogen atom, a methyl group or a phenyl group.)
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Paragraph 0046; 0050; 0051
(2018/02/10)
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- Organocatalyzed Trifluoromethylation of Ketones and Sulfonyl Fluorides by Fluoroform under a Superbase System
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Fluoroform (HCF3, HFC-23) is a side product in the manufacture of polytetrafluoroethylene (Teflon). Despite its attractive properties, taming HCF3 for trifluoromethylation is quite problematic owing to its low acidity and the labilit
- Okusu, Satoshi,Hirano, Kazuki,Tokunaga, Etsuko,Shibata, Norio
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p. 581 - 585
(2015/10/20)
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- Convenient stereoselective synthesis of β-perfluoroalkyl α,β-unsaturated esters via H?rner-Wadsworth-Emmons reactions
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Condensation of H?rner-Wadsworth-Emmons reagents 3 and ketones 2 with a perfluoroalkyl (Rf) moiety prepared in situ was proved to be significantly efficient and powerful methods for the construction of a wide variety of α,β-unsaturated esters with Rf and R1 groups both at the β-position due to convenient avoidance of usually tedious as well as troublesome isolation steps of these ketones 2.
- Yamazaki, Takashi,Mano, Noriko,Hikage, Reo,Kaneko, Tsutomu,Kawasaki-Takasuka, Tomoko,Yamada, Shigeyuki
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p. 8059 - 8066
(2015/12/30)
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- Development of (Trifluoromethyl)zinc Reagent as Trifluoromethyl Anion and Difluorocarbene Sources
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The trifluoromethylation of carbonyl compounds is accomplished by the stable (trifluoromethyl)zinc reagent generated and then isolated from CF3I and ZnEt2, which can be utilized as a trifluoromethyl anion source (CF3-). The reaction proceeds smoothly with diamine as a ligand and ammonium salt as an initiator, providing the corresponding trifluoromethylated alcohol products. Moreover, the (trifluoromethyl)zinc reagent can also be employed as a difluorocarbene source (:CF2) not only for gem-difluoroolefination of carbonyl compounds with phosphine but also for gem-difluorocyclization of alkenes or alkynes via the thermal decomposition, respectively.
- Aikawa, Kohsuke,Toya, Wataru,Nakamura, Yuzo,Mikami, Koichi
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supporting information
p. 4996 - 4999
(2015/11/03)
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- Polyfluoroalkylation of carbonyl compounds by polyfluoroalkyl anions generated from polyfluorocarboxamides
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Polyfluoroalkyl anions, generated by reduction of (polyfluoroalkanoyl)piperidines with Et3BHK, were used for the polyfluoroalkylation of carbonyl compounds. Trifluoromethylation of aromatic aldehydes proceeded in good yields, and that of aliphatic aldehydes afforded a moderate yield. In contrast, the yield was low when the reaction involved benzophenone. Pentafluoroethylation and octafluorobutylation of aldehydes were also carried out by using the corresponding (polyfluoroalkanoyl)piperidines, which were prepared from commercially available polyfluorocompounds. The (polyfluoroalkanoyl)piperidines were also prepared through polyfluorination, and were used in the polyfluoroalkylation of aldehydes.
- Wakita, Natshumi,Hara, Shoji
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p. 1201 - 1212
(2016/11/07)
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- DIRECT TRIFLUOROMETHYLATIONS USING TRIFLUOROMETHANE
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A direct trifluoromethylation method preferably using a trifluoromethane as a fluoro-methylating species. In particular, the present method is used for preparing a trifluoromethylated substrate by reacting a fluoromethylatable substrate with a trifiuoromethylating agent in the presence of an alkoxide or metal salt of silazane under conditions sufficient to trifluoromethylate the substrate; wherein the fluoromethylatable substrate includes chlorosilanes, carbonyl compounds such as esters, aryl halides, aldehydes, ketones, chalcones, alkyl formates, alkyl halides, aryl halides, alkyl borates, carbon dioxide or sulfur.
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Paragraph 0068
(2014/03/25)
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- Organocatalysis approach to trifluoromethylation with fluoroform
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The organic base methodology exploits an access to generate the "trifluoromethyl anion" for carbonyl, ester, acid halide, epoxide, deuterium donor, and carbon dioxide substrates to afford the trifluoromethylation products with good overall efficiency even in organocatalysis conditions. The NMR analysis of the mixture of fluoroform and P4-base shows no change thereof. However, on addition of electrophiles, the trifluoromethylation products were obtained efficiently.
- Zhang, Yuan,Fujiu, Motohiro,Serizawa, Hiroki,Mikami, Koichi
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supporting information
p. 367 - 371
(2014/01/06)
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- A sterically demanding organo-superbase avoids decomposition of a naked trifluoromethyl carbanion directly generated from fluoroform
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A simple strategy avoiding the decomposition of a naked trifluoromethyl anion to difluorocarbene by a sterically very demanding organo-superbase without the help of a trifluoromethyl anion reservoir such as DMF is reported. The direct non-metallic trifluoromethylation of carbonyl compounds using fluoroform in the presence of t-Bu-P4 base afforded trifluoromethyl alcohols in high yields.
- Kawai, Hiroyuki,Yuan, Zhe,Tokunaga, Etsuko,Shibata, Norio
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supporting information
p. 1446 - 1450
(2013/05/09)
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- Nucleophilic trifluoromethylation of carbonyl compounds: Trifluoroacetaldehyde hydrate as a trifluoromethyl source
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A feasible nucleophilic trifluoromethylating protocol has been developed using trifluoroacetaldehyde hydrate as an atom-economical trifluoromethyl source. The reaction was found to be applicable to the nucleophilic trifluoromethylation of a broad spectrum of carbonyl compounds with satisfactory yields in general. DFT calculations have been performed to provide mechanistic insight into the present and related reactions employing 2,2,2-trifluoro-1- methoxyethanol and hexafluoroacetone hydrate.
- Surya Prakash,Zhang, Zhe,Wang, Fang,Munoz, Socrates,Olah, George A.
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p. 3300 - 3305
(2013/06/27)
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- Amidinate salt of hexafluoroacetone hydrate for the preparation of fluorinated compounds by the release of trifluoroacetate
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A powerful, new reagent, an amidinate salt of hexafluoroacetone hydrate, is an air-stable salt that can be used for the preparation of fluorinated organic molecules. Nucleophilic trifluoromethylation reactions are demonstrated following the base-promoted release of trifluoroacetate. This reagent is soluble in many polar organic solvents and produces fluoroform, following the release of trifluoroacetate. Reactions with this reagent and common electrophiles provide excellent yields of trifluoromethylated products.
- Riofski, Mark V.,Hart, Allison D.,Colby, David A.
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supporting information
p. 208 - 211
(2013/04/10)
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- Taming of fluoroform: Direct nucleophilic trifluoromethylation of Si, B, S, and C centers
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Fluoroform (CF3H), a large-volume by-product of the manufacture of Teflon, refrigerants, polyvinylidene fluoride (PVDF), fire-extinguishing agents, and foams, is a potent and stable greenhouse gas that has found little practical use despite the growing importance of trifluoromethyl (CF3) functionality in more structurally elaborate pharmaceuticals, agrochemicals, and materials. Direct nucleophilic trifluoromethylation using CF3H has been a challenge. Here, we report on a direct trifluoromethylation protocol using close to stoichiometric amounts of CF3H in common organic solvents such as tetrahydrofuran (THF), diethyl ether, and toluene. The methodology is widely applicable to a variety of silicon, boron, and sulfur-based electrophiles, as well as carbon-based electrophiles.
- Surya Prakash,Jog, Parag V.,Batamack, Patrice T. D.,Olah, George A.
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p. 1324 - 1327
(2013/02/22)
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- COMPOSITIONS AND PROCESSES OF PREPARING AND USING THE SAME
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The present invention relates to compositions, for example, the DBU/Hexafluoroacetone hydrate salt, and processes of preparing and using the same for the modification of chemical compounds via the release of trifluoroacetate. The DBU/Hexafluoroacetone hydrate salt can perform trifluoromethylation reactions on chemical compounds, such as carbonyl group-containing compounds.
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Page/Page column 36
(2012/10/08)
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- Nucleophilic trifluoromethylation with organoboron reagents
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Potassium trialkoxy(trifluoromethyl)borates are shown to behave as convenient reagents for nucleophilic trifluoromethylation of non-enolizable aldehydes and N-tosylimines to give CF3-substituted alcohols and N-tosylamines in good yields.
- Levin, Vitalij V.,Dilman, Alexander D.,Belyakov, Pavel A.,Struchkova, Marina I.,Tartakovsky, Vladimir A.
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supporting information; experimental part
p. 281 - 284
(2011/02/26)
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- Alkoxide-induced nucleophilic trifluoromethylation using diethyl trifluoromethylphosphonate
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A novel alkoxide-induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides, and diselenides using diethyl trifluoromethylphosphonate is presented. In these reactions diethyl trifluoromethylphosphonate acts as a [CF3-] synthon.
- Cherkupally, Prabhakar,Beier, Petr
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experimental part
p. 252 - 255
(2010/03/24)
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- The rhodium-catalysed 1,2-addition of arylboronic acids to aldehydes and ketones with sulfonated S-Phos
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The rhodium-catalysed 1,2-addition of arylboronic acids to aryl aldehydes has been accomplished in high yield using sulfonated S-Phos, a water-soluble biaryl phosphine ligand which allows for catalyst recycling. The catalytic protocol has also been successful in the challenging arylation of ketones.
- White, James R.,Price, Gareth J.,Plucinski, Pawel K.,Frost, Christopher G.
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supporting information; experimental part
p. 7365 - 7368
(2010/03/03)
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- Unusual reactions of Grignard reagents toward fluoroalkylated esters
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Fluorine-containing esters were demonstrated to be convenient substrates for construction of the corresponding ketones by low temperature reaction with Grignard reagents followed by warming up to 0 °C, while heating the mixture up to 80 °C readily promoted the reduction of the ketones obtained by the generated magnesium alkoxides whose mechanism was speculated as Meerwein-Ponndorf-Verley type reduction by computational technique.
- Yamazaki, Takashi,Terajima, Tsukasa,Kawasaki-Taskasuka, Tomoko
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p. 2419 - 2424
(2008/09/18)
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- Some studies on nucleophilic trifluoromethylation using the shelf-stable trifluoromethylacetophenone-N,N-dimethyltrimethylsilylamine adduct
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The simple thermal addition product of N,N-dimethyltrimethylsilylamine with 2,2,2-trifluoroacetophenone provides a shelf-stable reagent for nucleophilic trifluoromethylation of both the carbonyl and the imine group.
- Motherwell, William B.,Storey, Lynda J.
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p. 491 - 498
(2007/10/03)
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- Trifluoromethanesulfinamide from ephedrine: A more efficient trifluoromethylating reagent
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Nucleophilic trifluoromethylation of non-enolizable and enolizable carbonyl compounds was achieved with the trifluoromethanesulfinamide derived from O-silylated ephedrine. In contrast to the trifluoroacetamide analog, previously described, this reagent is able to trifluoromethylate more acidic enolizable compounds.
- Roussel, Solveig,Billard, Thierry,Langlois, Bernard R.,Saint-Jalmes, Laurent
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p. 2119 - 2122
(2007/10/03)
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- METHODS FOR NUCLEOPHILIC FLUOROMETHYLATION
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A novel, convenient and efficient method for trifluoromethylation of substrate compounds is disclosed. Particularly, alkoxide and hydroxide induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides and other electrophiles, using phenyl trifluoromethyl sulfone PhSO2CF3 (or sulfoxide PhSOCF3) is disclosed. A method of both symmetrical and unsymmetrical anti-2,2-difluoropropan-1,3-diols with high diastereoselectivity (up to 94 % de) is disclosed using dufluoromethyl phenyl sulfone. This unusual type of high diastereoselectivity was obtained via an intramolecular charge-charge repulsion effect rather than the traditional steric control (based on the Cram's rule). Thus, difluoromethyl phenyl sulfone can be used as a novel difluoromethylene dianion species (`CF2""), which can couple two electrophiles (such as diphenyl disulfide or non-enolizable aldehydes) to give new difluoromethylenated products.
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- Alkoxide- and hydroxide-induced nucleophilic trifluoromethylation using trifluoromethyl sulfone or sulfoxide
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(Matrix presented) The first alkoxide- and hydroxide-induced nucleophilic trifluoromethylation of carbonyl compounds, disulfides, and other electrophiles, using phenyl trifluoromethyl sulfone 1a (sulfoxide 1b) is reported. The trifluoromethyl sulfone 1a or sulfoxide 1b acts as a CF3 - synthon. Both sulfone 1a and sulfoxide 1b are commercially available and can also be conveniently prepared from trifluoromethane. The new methodology provides a convenient route for efficient trifluoromethylation.
- Prakash, G. K. Surya,Hu, Jinbo,Olah, George A.
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p. 3253 - 3256
(2007/10/03)
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- Trifluoroacetophenone as nucleophilic trifluoromethylating reagent
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Trifluoroacetophenone can be used as nucleophilic trifluoromethylating reagent towards non-enolizable ketones by action of potassium tert-butoxide.
- Jablonski, Lukas,Billard, Thierry,Langlois, Bernard R.
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p. 1055 - 1057
(2007/10/03)
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- Trifluoroacetic acid derivatives as nucleophilic trifluoromethylating reagents
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Secondary trifluoroacetamides and alkyl trifluoroacetates can be used as nucleophilic trifluoromethylating reagents towards non-enolizable ketones by action of potassium tert-butoxide.
- Jablonski, Lukas,Joubert, Jér?me,Billard, Thierry,Langlois, Bernard R.
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p. 230 - 232
(2007/10/03)
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- Trifluoromethanesulfinic acid derivatives as nucleophilic trifluoromethylating reagents
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Secondary trifluoromethanesulfinamides and alkyl trifluoromethanesulfinates can be used as nucleophilic trifluoromethylating reagents towards various electrophiles by action of potassium tert-butoxide.
- Inschauspe, David,Sortais, Jean-Baptiste,Billard, Thierry,Langlois, Bernard R.
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p. 233 - 235
(2007/10/03)
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- Trifluoroacetamides from amino alcohols as nucleophilic trifluoromethylating reagents
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Both non-enolizable and enolizable carbonyl compounds underwent nucleophilic trifluoromethylation by a new family of cheap and efficient trifluoroacetamide reagents derived from vic-amino alcohols (see picture). From an ecological and an economic viewpoint these represent a promising alternative to other known trifluoromethylation reagents.
- Joubert, Jerome,Roussel, Solveig,Christophe, Carole,Billard, Thierry,Langlois, Bernard R.,Vidal, Thierry
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p. 3133 - 3136
(2007/10/03)
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- The trifluoromethylacetophenone-N,N-dimethyltrimethylsilylamine adduct - A new shelf stable reagent for nucleophilic trifluoromethylation
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The simple thermal addition product of N,N-dimethyltrimethylsilylamine with trifluoromethylacetophenone provides a shelf-stable reagent for nucleophilic trifluoromethylation of the carbonyl group.
- Motherwell, William B.,Storey, Lynda J.
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p. 646 - 648
(2007/10/03)
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- Nucleophilic trifluoromethylation using trifluoromethyl iodide. A new and simple alternative for the trifluoromethylation of aldehydes and ketones
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(Matrix Presented) A novel method for nucleophilic trifluoromethylation of aldehydes and ketones, based on photoinduced reduction of trifluoromethyl iodide by tetrakis(dimethylamino)ethylene (TDAE), is presented.
- Ait-Mohand, Samia,Takechi, Naoto,Medebielle, Maurice,Dolbier Jr., William R.
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p. 4271 - 4273
(2007/10/03)
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- Trifluoromethylation of nonenolizable carbonyl compounds with a stable piperazino hemiaminal of trifluoroacetaldehyde
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A new stable hemiaminal of fluoral (1) can easily be obtained from the methyl hemiketal of fluoral and N-benzylpiperazine. This white crystalline compound can be used under basic conditions as an efficient nucleophilic trifluoromethylating reagent towards nonenolizable carbonyl compounds.
- Billard, Thierry,Langlois, Bernard R.,Blond, Gaelle
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p. 1467 - 1471
(2007/10/03)
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- Nucleophilic trifluoromethylation of carbonyl compounds and disulfides with trifluoromethane and silicon-containing bases
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Provided that DMF (or another N,N-dialkylformamide) is present in the reaction medium, at least in a catalytic amount, fluoroform trifluoromethylates efficiently carbonyl compounds, even enolizable ones, when opposed to (TMS)2N- M+, generated in situ from N(TMS)3 and M+ F- or RO- Na+. When F- is used in a catalytic amount, silylated α-(trifluoromethyl)carbinols are obtained: In this case, the four-component system HCF3/N(TMS)3/catalytic F-/catalytic DMF behaves like the Ruppert's reagent, especially as far as nonenolizable carbonyl compounds are concerned (CF3SiMe3 remains more efficient for enolizable carbonyl compounds). This process involves an adduct between DMF and -CF3 which is the true trifluoromethylating agent. In the same way, fluoroform efficiently trifluoromethylates disulfides and diselenides when deprotonated with a strong base selected from t-BuOK or N(SiMe3)3/Me4NF (or TBAT). t-BuOK is more adapted to the trifluoromethylation of awl disulfides whereas N(SiMe3)3/F- is Well suited to that of aliphatic disulfides.
- Large,Roques,Langlois
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p. 8848 - 8856
(2007/10/03)
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- 19F nuclear magnetic resonance spectroscopy for the quantitative detection and classification of carbonyl groups in lignins
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A novel method that permits the quantitative detection and classification of various carbonyl groups in lignins has been developed. The proposed method was optimized with the quantitative trifluoromethylation of a series of carbonyl-containing lignin-like model compounds. This effort was followed by 19F NMR spectral analyses of the resulting fluorine derivatives allowing for a thorough understanding of their structure/19F chemical shift relationships. The various carbonyl groups present in lignins were also investigated by trifluoromethylating them in the presence of catalytic amounts of tetramethylammonium fluoride (TMAF), followed by hydrolysis with TMAF in tetrahydrofuran. By using a variety of selective reactions, it became possible to assign a number of prominent 19F NMR signals to a variety of carbonyl groups present in lignins. These studies demonstrated that the proposed method can be applied to the quantitative determination of carbonyl groups that are present in soluble native and technical lignins.
- Ahvazi, Behzad C.,Crestini, Claudia,Argyropoulos, Dimitris S.
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p. 190 - 201
(2007/10/03)
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- 19F Nuclear Magnetic Resonance Spectroscopy for the Elucidation of Carbonyl Groups in Lignins. 1. Model Compounds
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A new method for the detection of different classes of carbonyl groups in a series of carbonyl-containing lignin-like model compounds has been developed. The method is based on the selective fluoride-induced trifluoromethylation of carbonyl groups with (trifluoromethyl)trimethylsilane (TMS-CF3) in the presence of tetramethylammonium fluoride (TMAF), followed by hydrolysis with aqueous HF or TMAF in the case of quinones. In this study a series of ketones, aldehydes, quinones, and dimeric-lignin model compounds were quantitatively trifluoromethylated followed by 19F NMR spectral analyses of the resulting fluorine-containing derivatives, allowing for a thorough understanding of their structure/19F chemical shift relationships. These studies have shown that the 19F-NMR chemical shifts of the trifluoromethyl groups vary significantly and consistently for various classes of carbonyl groups which may be present in complex lignocellulosic materials. These studies are to form the basis for the development of a novel and sensitive method that can be used to obtain quantitative information on the various carbonyl groups present in such materials.
- Ahvazi, Behzad C.,Argyropoulos, Dimitris S.
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p. 2167 - 2175
(2007/10/03)
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- Quantitative trifluoromethylation of carbonyl-containing lignin model compounds
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The efficient trifluoromethylation of a series of carbonyl-containing lignin model compounds was made possible by using Ruppert's reagent in the presence of tetramethylammonium fluoride (TMAF), followed by hydrolysis with aqueous HF. These studies demonstrate that such a method can quantitatively convert carbonyl groups to the CF3-containing compounds, thus qualifying the procedure as a potential analytical tool for the determination of carbonyl groups in lignins.
- Ahvazi,Argyropoulos
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p. 195 - 198
(2007/10/03)
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- Electroreductive coupling of halofluoro compounds with aldehydes
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Electroreductive intermolecular coupling of halofluoro compounds such as 1,1,1-trichloro-2,2,2-trifluoroethane, methyl chlorodifluoroacetate, and perfluoroalkyl halides with aldehydes took place effectively in the presence of chlorotrimethylsilane and one of the coupling products, 2,2-dichloro-3,3,3-trifluoro-1-phenyl-1-propranol, was selectively convertible to a variety of compounds with using the electroreduction as a key reaction.
- Shono,Kise,Oka
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p. 6567 - 6570
(2007/10/02)
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- Electroorganic Chemistry. 130. A Novel Trifluoromethylation of Aldehydes and Ketones Promoted by an Electrogenerated Base
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A base generated by the electroreduction of 2-pyrrolidone deprotonated trifluoromethane to form a trifluoromethyl anion equivalent.In the presence of hexamethyldisilazane, this species reacted with a variety of aldehydes and ketones to afford (trifluoromethyl)-carbinols in high yield.
- Shono, Tatsuya,Ishifune, Manabu,Okada, Toshio,Kashimura, Shigenori
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- ELECTROCHEMICAL TRIFLUOROMETHYLATION OF CARBONYL COMPOUNDS
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The electroreduction of CF3Br in DMF containing aldehydes or ketones, using a sacrificial zinc anode, affords the corresponding trifluoromethyl alcohols together with the unreactive organozinc species CF3ZnBr and (CF3)2Zn.The alcohols are obtained with good yields from aldehydes.With ketones the organozinc species are formed preferentially to the alcohols, but the addition of tetramethylene-diamine allows the alcohols to form with moderate yields.
- Sibille, S.,Mcharek, S.,Perichon, J.
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p. 1423 - 1428
(2007/10/02)
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- Sterically Crowded Sulfonate Esters: Novel Leaving Groups with Hindered S-O Cleavage
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Reagents and procedures for the preparation of tert-butyl sulfonate esters 2 and 2,2,2-trifluoro-1,1-diphenylethane sulfonate esters 3 (TDE-sulfonates) are described.In these new sulfonates, S-O-scission is reduced significantly by steric hindrance.
- Netscher, Thomas,Prinzbach, Horst
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p. 683 - 688
(2007/10/02)
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- SOLVOLYTIC STUDIES OF THE HIGHLY CROWDED 1-ARYL-1-PHENYL-1-(TRIFLUOROMETHYL)METHYL BR0MIDE AND TOSYLATES
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In the titled system the remarkably high tosylate/bromide solvolysis rate ratio of 1.56E6:1 indicates a highly strained ground state, and the reverse order of reactivity for substrate having l-(4-trifluoromethyl)phenyl vs. that having 1-(3-trifluoromethyl
- Liu, Kwang-Ting,Kuo, Mann-Yan
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p. 355 - 358
(2007/10/02)
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