- C-F Bond Activation of a Perfluorinated Ligand Leading to Nucleophilic Fluorination of an Organic Electrophile
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We report a fluorine transfer reaction in which fluorine from a perfluorinated ligand undergoes C-F bond activation and transfers to an electrophile, resulting in the formation of a new fluorinated product and dimerization of the monodefluorinated complex. Treatment of [(η5,κ2C-C5Me4CH2C6F5CH2NC3H2NMe)-RhCl] with the organic electrophile, toluoyl chloride, resulted in the formation of a rhodium(III) metallocycle via C-F bond activation assisted defluorinative coupling. Fission of the C-F bond liberated nucleophilic fluoride, which converted acyl chloride to acyl fluoride. The overall reaction was monitored using a multivariate analysis approach in real time.
- Hanson-Heine, Magnus W. D.,Licence, Peter,Marr, Andrew C.,Morgan, Patrick J.,Saunders, Graham C.,Thomas, Hayden P.
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supporting information
p. 2116 - 2124
(2020/07/23)
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- Recyclable Organocatalysts for a One-Pot Asymmetric Synthesis of 2-Fluorocyclohexanols Bearing Six Contiguous Stereocenters
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A recyclable fluorous bifunctional Cinchona alkaloid/thiourea-catalyzed quadruple fluorination/Michael/Michael/aldol sequence has been developed for the one-pot synthesis of cyclohexanols bearing six contiguous stereocenters including a fluorinated tertiary carbon. By using readily available starting materials including β-keto esters, β-nitrostyrenes, and α,β-unsaturated aldehydes, fully functionalized cyclohexanols were synthesized in 52–80% yields with up to 99% ee and >20:1 dr. The fluorous catalyst could be easily recovered by fluorous solid-phase extraction in 94–97% yield and >98% purity. In addition to the high synthetic efficiency achieved through the pot economic reactions, other green techniques such as transition metal-free catalysis and catalyst recovery are also employed. (Figure presented.).
- Huang, Xin,Liu, Miao,Jasinski, Jerry P.,Peng, Bo,Zhang, Wei
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p. 1919 - 1926
(2017/06/09)
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- One-pot fluorination and Mannich reactions of 1,3-dicarbonyl compounds
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Abstract One-pot fluorination of 1,3-dicarbonyl compounds with Selectfluor followed by the Mannich reaction with anilines and benzaldehydes is developed for the synthesis of α-fluoro and aminomethylated 1,3-dicarbonyl compounds.
- Pham, Kenny,Huang, Xin,Zhang, Wei
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supporting information
p. 1998 - 2000
(2015/03/18)
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- AZAINDAZOLES
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Herein are disclosed azaindazoles of formula (I), (I), where the various groups are defined herein, and which are useful for treating cancer.
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Page/Page column 94.1
(2013/03/28)
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- One-pot fluorination followed by Michael addition or Robinson annulation for preparation of α-fluorinated carbonyl compounds
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Fluorination followed by the Michael addition or Robinson annulation of 1,3-dicarbonyl compounds is introduced for the synthesis of acyclic and cyclic α-fluoro-β-ketoesters and α-fluoro-1,3-diketones. The decarboxylation step can also be added to the reac
- Yi, Wen-Bin,Cai, Chun,Huang, Xin,Zhang, Wei
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p. 3185 - 3189,5
(2020/09/16)
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- Continuous gas/liquid-liquid/liquid flow synthesis of 4-fluoropyrazole derivatives by selective direct fluorination
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4-Fluoropyrazole systems may be prepared by a single, sequential telescoped two-step continuous gas/liquid-liquid/liquid flow process from diketone, fluorine gas and hydrazine starting materials.
- Breen, Jessica R.,Sandford, Graham,Yufit, Dmitrii S.,Howard, Judith A. K.,Fray, Jonathan,Bhairavi, Patel
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supporting information; experimental part
p. 1048 - 1054
(2011/10/05)
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- Microwave-mediated pyrazole fluorinations using selectfluor
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Microwave-mediated electrophilic fluorinations and a new single-pot condensation en route to ring-fluorinated pyrazoles were examined: chemical equation represented The monofluorination by these methods was successful for a variety of pyrazoles, with yields ranging from 13% to 75%. While electrophilic aromatic fluorination of 3-CF3 pyrazoles proved largely ineffective, development ofa single-pot process overcame this limitation. The microwave-mediated reaction is regioselective; ring fluorination of the heterocycle occurs preferentially over phenyl and alkyl substituents. Alkyl side chain fluorination, when desired, can be modulated by reactant ratios. The single-pot method, which involves acid catalysis by H-TEDA, produces 4-fluoropyrazoles products.
- Sloop, Joseph C.,Jackson, James L.,Schmidt, Robert D.
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scheme or table
p. 341 - 345
(2010/08/05)
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- Reactions of trifluoroamine oxide: A new method for selective fluorination of 1,3-diketones and β-ketoesters
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Fluorination of 1,3-diketones and β-ketoesters with trifluoroamine oxide in the presence of tetrabutylammonium hydroxide (TBAH) provides a one step route to mono- and difluoro-products selectively fluorinated at the α-position in good yields.
- Gupta, Om D.,Shreeve, Jean'ne M.
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p. 2799 - 2801
(2007/10/03)
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- Preparation of fluorinated dicarbonyls
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PCT No. PCT/GB94/02547 Sec. 371 Date Feb. 21, 1997 Sec. 102(e) Date Feb. 21, 1997 PCT Filed Nov. 18, 1994 PCT Pub. No. WO95/14646 PCT Pub. Date Jun. 1, 1995A method for the fluorination of 1,3-diketones and 1,3-ketoesters is disclosed.
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- Direct fluorination of 1,3-dicarbonyl compounds
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In acid media, 1,3-diketones and 1,3-keloesters can be fluorinated in high yield and often with high conversion mainly to the corresponding 2-fluoro- compounds. Diesters such as diethyl malonate do not react with fluorine under the same reaction conditions. The mechanism of these reactions has been investigated and while the identity of the electrophilic fluorinating species is uncertain, we believe that the essential features of the reaction pathway are understood. Copyright
- Chambers, Richard D.,Greenhall, Martin P.,Hutchinson, John
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- Direct Fluorination of 1,3-Dicarbonyl Compounds
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1,3-Dicarbonyls, such as 1,3-diketones and 1,3-ketoesters, react directly with elemental fluorine at room temperature to give the corresponding 2-fluoro- and, in some cases, 2,2-difluoro-compounds in high yield.
- Chambers, Richard D.,Greenhall, Martin P.,Hutchinson, John
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- Ring-fluorinated pyrazoles
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2-Fluoro-1,3-diketones react with phenylhydrazine to yield ring-fluorinated pyrazoles in high yield.An isoxazole is produced when 2-fluoro-1,3-diphenyl-1,3-propandione is treated with hydroxylamine hydrochloride,
- Bumgardner, Carl L.,Sloop, Joseph C.
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p. 141 - 146
(2007/10/02)
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- Room-temperature Reactions of CsSO4F with Organic Molecules containing Heteroatoms
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Room-temperature fluorination of pentane-2,4-dione with CsSO4F gave 3-fluoro and 1,3-difluoro derivatives, while 5,5-difluorobarbituric acid was formed in high yield in a 2 h reaction at 100 deg C; 1,3-dimethyluracil was converted in methanol via cis- and trans-5-fluoro-6-methoxy derivatives into 5-fluoro-1,3-dimethyluracil in high yield and uridine into 5-fluorouridine.
- Stavber, Stojan,Zupan, Marko
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p. 563 - 564
(2007/10/02)
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- Room Temperature Fluorination of 1,3-Diketones and Enol Acetates with Xenon Difluoride
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Fluorination of 1,3-diketones with xenon difluoride in the presence of the insoluble cross-linked polystyrene-4-vinylpyridine complex with boron trifluoride and insoluble cross-linked polystryrene-4-vinylpyridine resins resulted in the formation of mono- and di-fluoro products, while reactions with enol acetates in the presence of hydrogen fluoride gave α-fluoroketones.
- Zajc, Barbara,Zupan, Marko
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p. 759 - 760
(2007/10/02)
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