16519-02-1Relevant articles and documents
A Unified and Desymmetric Approach to Chiral Tertiary Alkyl Halides
Huang, Zhongxing,Low, Kam-Hung,Zhang, Suihan,Zheng, Yin,Zi, Weiwei
supporting information, p. 1951 - 1961 (2022/02/09)
Enantioenriched tertiary alkyl halides are prevalent in bioactive molecules and can serve as versatile synthetic intermediates to construct complex structures. While conventional access to these motifs often hinges on stereoselective carbon-halogen or carbon-carbon bond formation reactions, desymmetric approaches using halogenated and prochiral tetrasubstituted carbons are largely elusive in comparison. Here, we report that a suite of dinuclear zinc catalysts with a prolinol- or pipecolinol-derived tetradentate ligand can reductively desymmetrize a large collection of easily available halomalonic esters to α-halo-β-hydroxyesters. These polyfunctionalized tertiary alkyl fluorides, chlorides, and bromides proved to be useful intermediates toward fluorinated drug analogs and polyhalogenated monoterpenes. The facile intramolecular epoxidation of the chiral chloride and bromide products has also enabled expeditious access to natural products containing tertiary alcohol motifs.
New promising lithium malonatoborate salts for high voltage lithium ion batteries
Sun, Xiao-Guang,Wan, Shun,Guang, Hong Yu,Fang, Youxing,Reeves, Kimberly Shawn,Chi, Miaofang,Dai, Sheng
, p. 1233 - 1241 (2017/02/05)
Three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonatoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonatoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoromalonatoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF4 and LiPF6. Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi0.5Mn1.5O4 (LNMO) to form effective solid electrolyte interphases (SEIs). In addition, these new salt-based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi0.5Mn1.5O4 and graphite based half-cells and full cells.
HETEROARYL COMPOUNDS AS IRAK INHIBITORS AND USES THEREOF
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Paragraph 00180, (2017/05/02)
The present invention relates to compounds of Formula (I) and pharmaceutically acceptable compositions thereof, useful as IRAK inhibitors.
HETEROARYL COMPOUNDS AS IRAK INHIBITORS AND USES THEREOF
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Paragraph 00160, (2017/04/11)
The present invention relates to compounds of Formula (I) and pharmaceutically acceptable compositions thereof, useful as IRAK inhibitors.
METHOD FOR PRODUCING FLUOROMALONIC ESTER DERIVATIVE
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Paragraph 0031-0033, (2017/02/24)
PROBLEM TO BE SOLVED: To provide a method for producing a fluoromalonic ester derivative, useful as a raw material of electronic materials and as a synthetic intermediate of an agrochemical, which does not use or waste an expensive fluorinating agent and also has a short process. SOLUTION: A fluoromalonic ester derivative represented by a formula (2) is produced by reacting a malonic ester derivative with the 2-position modified with R3 with N-fluoro-bis(methanesulfonyl)imide in the presence of a Lewis acid. (R1 and R2 are each independently a methyl group, an ethyl group, a C3-4 linear, branched or cyclic alkyl group, a phenyl group, or a benzyl group; and R3 is H, a methyl group or an ethyl group.) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
Methyl NFSI: Atom-economical alternative to NFSI shows higher fluorination reactivity under Lewis acid-catalysis and non-catalysis
Fukushi, Kazunobu,Suzuki, Satoru,Kamo, Tomohiro,Tokunaga, Etsuko,Sumii, Yuji,Kagawa, Takumi,Kawada, Kosuke,Shibata, Norio
supporting information, p. 1864 - 1868 (2016/04/19)
Me-NFSI was first reported in 1994. Despite its atom-economical structure and similarity to a well-explored fluorinating reagent, NFSI, Me-NFSI has not appeared in the literature in over 20 years. We disclose that Me-NFSI is more effective for the fluorination of active methines under Lewis acid-catalysis and non-catalysis than NFSI.
A stable fluorinated and alkylated lithium malonatoborate salt for lithium ion battery application
Wan, Shun,Jiang, Xueguang,Guo, Bingkun,Dai, Sheng,Goodenough, John B.,Sun, Xiao-Guang
supporting information, p. 9817 - 9820 (2015/06/16)
A new fluorinated and alkylated lithium malonatoborate salt, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), has been synthesized for lithium ion battery application. A 0.8 M LiBMFMB solution is obtained in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt). The new LiBMFMB based electrolyte exhibits good cycling stability and rate capability in LiNi0.5Mn1.5O4 and graphite based half-cells.
Are carboxylic esters really refractory to DAST? On the fluorination of α-hydroxyesters with DAST
Lepri, Susan,Buonerba, Federica,Maccaroni, Paola,Goracci, Laura,Ruzziconi, Renzo
supporting information, p. 82 - 91 (2015/04/27)
Diethyl 2-alkyl-2-hydroxymalonates react with DAST almost exclusively at the ester carbonyl giving a mixture of ethyl 2-(ethoxydifluoromethyl)-2-hydroxyalkanoates, 1,1-bis(ethoxydifluoromethyl)alkan-1-ols when administered at room temperature in dichloromethane. The reaction was exploited in the synthesis of nucleus- and side-chain polyfluorinated indoles. The fluorination of substituted diethyl 2-[(1-tert-butoxycarbonylindol-3-yl)methyl]-2-hydroxymalonates with DAST gave a mixture of ethyl 2-(ethoxydifluoromethyl)-2-hydroxy-3-(1-tert-butoxycarbonylindol-3-yl)propionate, diastereomeric 1′-tert-butoxycarbonyl-2′-hydroxy-2,2-diethoxycarbonylspiro(cyclopropane-1,3′-indoline) and only traces of 1,1-bis(ethoxydifluoromethyl)-2-(1-tert-butoxycarbonylindol-3-yl)ethanol. The composition of these mixtures changes depending on the reaction conditions. Regioselectively substituted ethyl 2-hydroxy-2-[(1-tert-butoxycarbonylindol-3-yl)methyl]-3,3,3-trifluoropropionate reacts with DAST at 0 °C in dichloromethane giving satisfactory yields of the corresponding 1-ethoxy-2-[(1-tert-butoxycarbonylindol-3-yl)methyl]-1,1,3,3,3-pentafluoropropan-2-ols as the exclusive reaction products. In the same reaction conditions, ethyl 3-(1-tert-butoxycarbonylindol-3-yl)-2-hydroxypropionate mainly provides 1′-tert-butoxycarbonyl-2′-hydroxy-2,2-diethoxycarbonylspiro(cyclopropane-1,3′-indoline) together with the “normal” fluorination product ethyl 3-(1-tert-butoxycarbonylindol-3-yl)-2-fluoropropionate. A plausible mechanism of this process is proposed in the following.
A Convenient Synthesis of 2-Fluoro- and 2-Chloromalonic Esters Mediated by Hypervalent Iodine
Kitamura, Tsugio,Muta, Kensuke,Oyamada, Juzo
, p. 3241 - 3245 (2015/10/19)
Direct fluorination of malonic esters with a reagent system of iodosylbenzene and Et3N·5HF gave the corresponding 2-fluoromalonic esters in good to high yields. Direct chlorination using iodosylbenzene and hydrochloric acid also provided the 2-chloromalonates in high yields.
METHOD OF PRODUCING MONOFLUOROMALONIC ACID DERIVATIVE
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Paragraph 0046-0049, (2017/02/24)
PROBLEM TO BE SOLVED: To provide a method of producing a monofluoromalonic acid ester derivative that has a high yield, facilitates separation of a product, and allows industrial production. SOLUTION: A malonic acid ester derivative (1) is reacted with a hydrogen fluoride source in the presence of an iodosylbenzene derivative or an iodobenzene derivative and an oxidizing agent, to produce a monofluoromalonic acid derivative (4). COPYRIGHT: (C)2015,JPOandINPIT
