- Mechanochemical electrophilic fluorination of liquid beta-ketoesters
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An improved substrate scope for the mechanochemical electrophilic fluorination of dicarbonyls is reported. The applicable substrates have now been broadened to include liquid β-ketoesters. Key to this capability is the inclusion of a grinding auxiliary (NaCl) to improve mass transfer and prevent pasting or gumming of the reaction mixture. Notably, the use of a small amount of acetonitrile is critical to increasing the rate of reaction, ensuring complete consumption of starting materials during the short reaction times as well as improving the selectivity for the monofluorinated product in the mill.
- Howard, Joseph L.,Sagatov, Yerbol,Browne, Duncan L.
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p. 3118 - 3123
(2017/12/26)
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- The enantioselective addition of 1-fluoro-1-nitro(phenylsulfonyl)methane to isatin-derived ketimines
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An asymmetric organocatalytic addition of fluorinated phenylsulfonylnitromethane to isatin-derived ketimines was developed. The reaction was efficiently catalyzed by a chiral tertiary amine, cinchonine. This methodology provides a new type of optically active compound with two adjacent quaternary carbon stereocenters in good yield (up to 96%), with moderate diastereoselectivity (up to 5.7:1 dr) and excellent enantioselectivity (up to 98/96% ee).
- Urban,Franc,Hofmanová,Císa?ová,Vesely
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supporting information
p. 9071 - 9076
(2017/11/14)
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- A synthetic fluorine-containing acyclonucleosides analogues method
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The invention discloses a method for synthesizing fluorine-containing noncyclic nucleoside analog. The reaction equation is shown in the specification, wherein R1 is selected from one of methoxyl, ethyoxyl, piperidine, morpholine, dimethylamino and phenme
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Paragraph 0024-0026
(2017/02/28)
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- 1-BROMO-1-FLUOROBIS(PHENYLSULFONYL)METHANE, MANUFACTURING METHOD THEREOF AND MANUFACTURING METHOD OF 1-FLUOROBIS(PHENYLSULFONYL)METHANE USING THE SAME
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PROBLEM TO BE SOLVED: To provide 1-bromo-1-fluorobis(phenylsulfonyl)methane useful as a raw material for an industrial production of 1-fluorobis(phenylsulfonyl)methane useful as a synthesis raw material for pharmaceutical and agricultural chemical interme
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Paragraph 0035-0036
(2016/12/22)
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- Mono and difluorination of centers α to sulfonates and phosphonates using AcOF
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Acetyl hypofluorite, made easily from diluted fluorine and AcONa is very efficient in fluorinating anionic centers. Compounds containing the moieties CH2SO2 or COCH2PO react with bases to create the corresponding anions wh
- Vints, Inna,Gatenyo, Julia,Rozen, Shlomo
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- Organocatalytic alkynylation of densely functionalized monofluorinated derivatives: C(sp3)-C(sp) coupling
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Organocatalytic alkynylation of nucleophilic fluorocarbons using hypervalent iodine compounds under cinchona-based catalysis, namely using O-allyl N-anthracenyl cinchona alkaloid derivative II, is described. The reaction gives the final fluoro-propargyl compounds in good to excellent yields (up to 91%) and with moderate to low enantioselectivity (up to 61% ee). The reaction represents the first example of the use of hypervalent iodine compounds for the construction of fluorinated compounds and opens access to the preparation of biologically attractive compounds such as 1,2,3-triazoles.
- Kamlar, Martin,Putaj, Piotr,Vesely, Jan
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supporting information
p. 2097 - 2100
(2013/04/24)
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- Efficient synthesis of α-(fluoro/chloro/methoxy)disulfonylmethane derivatives as tunable substituted methyl synthons via a new C-S bond forming strategy
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A new synthetic protocol for the preparation of α-fluoro(disulfonyl) methane and its chloro as well as methoxy analogues has been developed. Due to the synthetic utility of α-fluoro(bisphenylsulfonyl)methane (FBSM) as a versatile synthon in the preparatio
- Prakash, G.K. Surya,Wang, Fang,Ni, Chuanfa,Thomas, Tito Joe,Olah, George A.
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experimental part
p. 1007 - 1012
(2010/11/16)
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- Synthesis of fluorinated β-ketosulfones and gem-disulfones by nucleophilic fluoroalkylation of esters and sulfinates with di- and monofluoromethyl sulfones
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(Chemical Equation Presented) An efficient and practically useful method for the preparation of α-functionalized mono- and difluoro(phenylsulfonyl) methanes by using a nucleophilic fluoroalkylation methodology was developed. α,α-Difluoro-β-ketosulfones, α
- Ni, Chuanfa,Zhang, Laijun,Hu, Jinbo
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supporting information; experimental part
p. 3767 - 3771
(2009/09/30)
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- Nucleophilic fluoroalkylation of α,β-enones, arynes, and activated alkynes with fluorinated sulfones: Probing the hard/soft nature of fluorinated carbanions
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(Chemical Equation Presented) We have successfully accomplished the nucleophilic fluoroalkylation of α,β-enones, arynes, and activated alkynes with fluorinated sulfones. It was found that for acylic α,β-enones, although the reaction medium and the structure of the enones can all influence the regioselectivity of the nucleophilic alkylation reactions, the hard/soft nature of the carbanions played a major role. By using the 1,4- and 1,2-addition product ratio as a probe to determine the hard/soft nature of the above-mentioned four halogenated carbanions, the order of the softness of these carbanions can be given as follows: [(PhSO2) 2CF-] (20) ≈ PhSO2CCl2 - (32) > PhSO2CHF- (31) > PhSO 2CF2- (30). In the case of fluoroalkylation of aryne (35 as the precursor) and α,β-acetylenic ketones 46 with fluorobis(phenylsulfonyl)methane (21), fluorobis(phenylsulfonyl)methylated arenes 36 and β-fluorobis(phenylsulfonyl)methylated α,β-enones 47 were obtained as the corresponding products in good yields. During the reaction between 2-fluoro-2-(phenylsulfonyl)acetophenone (34) and arynes or activated alkynes 46, an intramolecular tandem reaction process leads to the formation of acyl-fluoroalkylated arenes 43 or α-acyl-β- fluoroalkylated α,β-enones 48. It turned out that the softness of a fluorine-bearing carbanion (such as 20 or 33 derived from 21 or 34) plays a crucial role for the success of the nucleophilic fluoroalkylation reactions with arynes and some activated alkynes (α,β-acetylenic ketones).
- Ni, Chuanfa,Zhang, Laijun,Hu, Jinbo
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p. 5699 - 5713
(2008/12/21)
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- 1-FLUORO-1,1-BIS(PHENYLSULFONYL)METHANE AND METHOD FOR PRODUCING SAME
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A novel 1-fluoro-1,1-bis(arylsulfonyl)methane is provided which is useful in monofluoromethylation. Also provided is a production method thereof. A method for producing a fluorobis(arylsulfonyl)methane, the method including the steps of: treating a bis (a
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Page/Page column 5-6
(2008/12/09)
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- Regioselective electrochemical monofluorination of α-sulfonyl sulfides
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Highly regioselective monofluorination of α-sulfonyl sulfides was successfully carried out using anodic oxidation to provide the corresponding α-fluorinated products in moderate yields. The fluorinated products would be versatile fluorine-containing build
- Nagura, Hirokatsu,Fuchigami, Toshio
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experimental part
p. 1714 - 1718
(2009/04/07)
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- Fluorobis(phenylsulfonyl)methane: A fluoromethide equivalent and palladium-catalyzed enantioselective allylic monofluoromethylation
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Selective introduction of fluorine: Monofluoromethylation with the fluoromethide equivalent fluorobis(phenylsulfonyl)methane (1) was crucial in the syntheses of the pharmacologically important compounds monofluorinated (S)-ibuprofen ((S)-2) and 5-deoxy-5-
- Fukuzumi, Takeo,Shibata, Norio,Sugiura, Masayoshi,Yasui, Hiroyuki,Nakamura, Shuichi,Toru, Takeshi
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p. 4973 - 4977
(2007/10/03)
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- Nucleophilic fluoroalkylation of epoxides with fluorinated sulfones
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The unprecedented nucleophilic fluoroalkylation of simple epoxides with fluorinated sulfones was achieved to give the β-fluoroalkyl alcohols in one step. The negative "fluorine effect" in the nucleophilic fluoroalkylation of epoxides with fluorinated carbanions was probed by the reactivity comparison between carbanions PhSO2CF2 - (3) and PhSO2CCl2- (4) and between carbanions PhSO2CHF- (7) and PhSO2CHCl - (13). The mediation of this fluorine effect by introducing another electron-withdrawing benzenesulfonyl group was found to be an effective way to significantly increase the nucleophilicity of the fluorinated carbanions, with the reactivity order [(PhSO2)2CF-] (16) > PhSO2CFH- (7) ? PhSO2CF2 - (3).
- Ni, Chuanfa,Li, Ya,Hu, Jinbo
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p. 6829 - 6833
(2007/10/03)
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