- DARSTELLUNG VON PRIMAEREN ALKYLFLUORIDEN UNTER EINSATZ DER PHASEN TRANSFER KATALYSE
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The influence of the following factors on the solid-liquid PTC fluorination reaction of primary alkyl halides was studied: the catalyst quantity applied, the water content of solid alkali fluoride salt, and the type of catalyst.Kinetic curves at different temperatures were found for the reaction.The maximum yield is a function of the interaction of two parallel running reactions, namely the direct fluorination reaction and the catalyst decomposition.
- Dermiek, Salman,Sasson, Yoel
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Read Online
- Efficient protocol for the SO2F2-mediated deoxyfluorination of aliphatic alcohols
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Alkyl fluorides are prevalent in both the pharmaceutical and agrochemical industries. As such, there has been significant interest over the past 40 years in the development of new synthetic methods to access these important fluorinated motifs. Herein we report the sulfuryl fluoride-mediated deoxyfluorination of alcohols using room temperature reaction conditions in only an hour. A wide range of primary aliphatic alcohols were efficiently converted to the corresponding fluoride in 46-70% isolated yields. Secondary alcohols were also effectively deoxyfluorinated in 50–92% yields. Chiral secondary alcohols were cleanly converted to the corresponding alkyl fluoride with only a minor deterioration of the enantioenrichment. A steroid derivative also underwent deoxyfluorination in 50% yield and 5.9:1 dr, with the major product resulting from net inversion of the stereocenter.
- Epifanov, Maxim,Lai, Joey,Lee, Cayo,Sammis, Glenn M.,Wang, Cindy Xinyun
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supporting information
(2021/09/28)
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- Synthesis, Characterization, and Reactivity of Thermally Stable Anhydrous Quaternary Ammonium Fluorides
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The synthesis and properties of a new class of anhydrous quaternary ammonium fluorides, based on the rigid skeleton azabicyclo[2.2.2]octane, is described. Compounds 2a-d were easily prepared by passing the corresponding ammonium iodides over fluoride-based resin followed by drying their hydrated form at 100 or 140 °C under reduced pressure. The stability (experimental and theoretical study), solubility, reactivity, and characterization by solution and solid-state MAS NMR are discussed.
- Elias, Shlomi,Karton-Lifshin, Naama,Yehezkel, Lea,Ashkenazi, Nissan,Columbus, Ishay,Zafrani, Yossi
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supporting information
p. 3039 - 3042
(2017/06/23)
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- Stereospecific Electrophilic Fluorination of Alkylcarbastannatrane Reagents
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We report the use of isolable primary and secondary alkylcarbastannatrane nucleophiles in site-specific fluorination reactions. These reactions occur without the need for transition metal catalysis or in situ activation of the nucleophile. In the absence of the carbastannatrane backbone, alkyltin nucleophiles exhibit no activity towards fluorination. When enantioenriched alkylcarbastannatranes are employed, fluorination occurs predominately via a stereoinvertive mechanism to generate highly enantioenriched alkyl fluoride compounds. These conditions can also be extended to stereospecific chlorination, bromination, and iodination reactions.
- Ma, Xinghua,Diane, Mohamed,Ralph, Glenn,Chen, Christine,Biscoe, Mark R.
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supporting information
p. 12663 - 12667
(2017/09/11)
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- Selective mono-acylation of 1,2- and 1,3-diols using (α,α- difluoroalkyl)amines
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In the reaction of N,N-diethyl-α,α-difluorobenzylamine (DFBA) with 1,2- or 1,3-diols, selective mono-benzoylation occurs to afford mono-esters of the diols in good yield. The reaction is completed under mild conditions in a short reaction time. Further, prim-, sec-, and tert-diols and catechol can be converted to the corresponding mono-benzoates. DFBA is used for the protection of the hydroxy group in sugars. The selective mono-nicotinylation, formylation and pivaloylation of diols are also performed by using the corresponding difluoroalkylamines.
- Wakita, Natsumi,Hara, Shoji
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scheme or table
p. 7939 - 7945
(2010/10/19)
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- Preparation of Mono-/Difluorinated Hydrocarbon Compounds
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Mono- or difluorinated hydrocarbon compounds are prepared from an alcohol or a carbonylated compound by reacting one of these with a fluorinating reagent, optionally in the presence of a base, the fluorinating agent comprising a pyridinium reactant having the following formula (F), wherein R0 is an alkyl or cycloalkyl radical:
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Page/Page column 9
(2009/09/28)
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- DEHYDROXYLATED FLUORINATING AGENT
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There is provided a novel, useful dehydroxyfluorination agent containing sulfuryl fluoride (SO2F2) and an organic base that is free from a free hydroxyl group in the molecule. According to the present dehydroxyfluorination agent, it is not necessary to use perfluoroalkanesulfonyl fluoride, which is not preferable in large-scale use, and it is possible to advantageously produce optically-active fluoro derivatives, which are important intermediates of medicines, agricultural chemicals and optical materials, for example, 4-fluoroproline derivatives, 2'-deoxy-2'-fluorouridine derivatives, optically-active α-fluorocarboxylate derivatives, and monofluoromethyl derivatives, even in large scale.
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Page/Page column 19
(2009/03/07)
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- PROCESS FOR PRODUCTION OF FLUORO DERIVATIVE
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A fluoro derivative can be produced by reacting a hydroxy derivative with sulfuryl fluoride (SO2F2) in the presence of an organic base or in the presence of an organic base and a salt or complex composed of an organic base and hydrogen fluoride. This process enables to advantageously produce an optically active fluoro derivative (e.g., a 4-fluoroproline derivative, a 2'-deoxy-2'-fluorouridine derivative and an optically active α-fluorocarboxylate ester derivative) which is an important intermediate for the production of a pharmaceutical or agricultural agent or an optical material, even in large quantity without using a perfluoroalkanesulfonyl fluoride which is undesirable for industrial applications.
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Page/Page column 31
(2008/06/13)
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- Fluorination of carbinols with 2,2-difluoro-1,3-dimethylimidazolidine in ionic liquid
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The utility of ionic liquids for fluorination using 2,2-difluoro-1,3-dimethylimidazolidine (DFI) is described. Further, the fluorination of chiral epoxyalcohols gave the chiral monofluoromethylated epoxides.
- Kitazume, Tomoya,Ebata, Takuma
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p. 1509 - 1511
(2007/10/03)
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- Process for the production of fluorinated organic compounds and fluorinating agents
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A process for the production of a fluorinated organic compound, characterized by fluorinating an organic compound having a hydrogen atoms using IF5; and a novel fluorination process for fluorinating an organic compound having a hydrogen atoms by using a fluorinating agent containing IF5 and at least one member selected from the group consisting of acids, bases, salts and additives.
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- Novel fluorination reagent: IF5/Et3N-3HF
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IF5 in Et3N-3HF was found to be a stable, non-hazardous, easy to handle, and inexpensive reagent that enables effective and selective fluorination of organic compounds under mild conditions.
- Yoneda, Norihiko,Fukuhara, Tsuyoshi
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p. 222 - 223
(2007/10/03)
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- Deiodinative fluorination of alkyl iodide with p-iodotoluene difluoride
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Oxidative fluorination of alkyl iodides with p-iodotoluene difluoride (4) was carried out. In the presence of Et3N-4HF, the fluorination reaction of prim-alkyl iodides selectively took place at the iodine position under mild conditions to give the corresponding alkyl fluorides in good yields.
- Sawaguchi, Masanori,Hara, Shoji,Nakamura, Yutaka,Ayuba, Shinichi,Fukuhara, Tsuyoshi,Yoneda, Norihiko
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p. 3315 - 3319
(2007/10/03)
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- Electrochemical fluorodeiodination of alkyl iodides
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Electrochemical oxidation of alkyl iodides using Et3N-nHF complexes as an electrolyte proceeds under mild conditions to give alkyl fluorides in good yields. The reaction is highly chemoselective and the functional groups in the substrate such as an ester, ketone, chloride, and tosylate could be tolerated under the reaction conditions.
- Sawaguchi, Masanori,Ayuba, Shinichi,Nakamura, Yutaka,Fukuhara, Tsuyoshi,Hara, Shoji,Yoneda, Norihiko
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p. 999 - 1000
(2007/10/03)
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- TETRABUTYLAMMONIUM BIFLUORIDE: A VERSATILE AND EFFICIENT FLUORINATING AGENT
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The use of tetrabutylammonium bifluoride as stable and easily available source of fluoride ion in nucleophilic substitution processes with different substrates is reported.
- Bosch, Pilar,Camps, Francisco,Chamorro, Esther,Gasol, Vicens,Guerrero, Angel
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p. 4733 - 4736
(2007/10/02)
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- THE FLUORINATION OF ORGANIC SUBSTRATES WITH TETRAPHENYLPHOSPHONIUM HYDROGENDIFLUORIDE
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Tetraphenylphosphonium hydrogendifluoride acts as a powerful source of F- in various reactions with organic substrates to give fluorine containing products.
- Brown, S. J.,Clark, J. H.
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p. 251 - 258
(2007/10/02)
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- The efficiency of diphenylalkylsulfonium salts as alkylating agents
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A series of the title reagents have been used for the alkylation of a number of nucleophiles including iodide, cyanide, thiocyanate and fluoride ions as well as ethyl acetoacetate, phenylacetonitrile and a variety of nitrogen heterocyclic compounds.The results compared favorably with literature methods.
- Badet, Bernard,Julia, Marc,Lefebvre, Christian
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p. 431 - 434
(2007/10/02)
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