- Efficient synthesis of a new, highly versatile chiral derivatizing agent, α-cyano-α-fluoro-p-tolylacetic acid (CFTA)
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The new and versatile chiral derivatizing agent, α-cyano-α-fluoro-p-tolylacetic acid (CFTA), has been efficiently synthesized in optically pure form by Candida rugosa lipase-mediated kinetic resolution of racemic CFTA ethyl ester, the latter being readily
- Takeuchi, Yoshio
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- AlCl3 catalyzed coupling of: N-benzylic sulfonamides with 2-substituted cyanoacetates through carbon-nitrogen bond cleavage
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A new cross-coupling reaction of N-benzylic sulfonamides with 2-substituted cyanoacetates for the synthesis of 2-substituted benzylbenzene was reported. In the presence of AlCl3, a broad range of N-benzylic sulfonamides reacted smoothly with 2-substituted cyanoacetates to afford structurally diverse benzylbenzenes in moderate to excellent yields. The conversion could be enlarged to gram-scale efficiently. The practicability of this approach was further manifested in the synthesis of a related bioactive agent with high anti-inflammatory activity.
- Hu, Chen,Hong, Gang,Qian, Xiaofei,Kim, Kwang Rim,Zhu, Xiaoyan,Wang, Limin
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supporting information
p. 4984 - 4991
(2017/07/10)
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- Synergistic effect of a bis(proazaphosphatrane) in mild palladium-catalyzed direct α-arylations of nitriles with aryl chlorides
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The effect of a bis(proazaphosphatrane) ligand on the palladium-catalyzed direct α-arylation of nitriles with various aryl chlorides under mild conditions is reported. Comparisons of the catalytic properties of this ligand with those of three related mono(proazaphosphatrane)s under the same reaction conditions revealed that bis(proazaphosphatrane) displayed a synergistically enhanced activity. In the presence of the bis(proazaphosphatrane) ligand, ethyl cyanoacetate and primary as well as secondary nitriles were efficiently coupled with a wide variety of aryl chlorides that contained electron-rich, electron-poor, and electron-neutral groups.
- Han Kim, So,Jang, Wonseok,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 6025 - 6029
(2015/03/30)
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- Metal-free photochemical aromatic perfluoroalkylation of α-cyano arylacetates
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We report here an operationally simple protocol for the direct aromatic perfluoroalkylation and trifluoromethylation of α-cyano arylacetates. This metal-free approach, which occurs at ambient temperature and under visible-light irradiation, is driven by t
- Nappi, Manuel,Bergonzini, Giulia,Melchiorre, Paolo
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supporting information
p. 4921 - 4925
(2014/05/20)
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- Construction of 1,2,5-tricarbonyl compounds using methyl cyanoacetate as a glyoxylate anion synthon combined with copper(I) iodide-catalyzed aerobic oxidation
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A practical and efficient synthesis of various 1,2,5-tricarbonyl compounds is described. The synthesis has been carried out by a conjugate addition of methyl cyanoacetate to the β-position of α,β-unsaturated carbonyl compounds and a subsequent copper(I) iodide-catalyzed aerobic oxidation. In addition, various α-aryl- and α-alkyl-α-keto esters have been synthesized using a similar approach. Copyright
- Kim, Se Hee,Kim, Ko Hoon,Kim, Jae Nyoung
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supporting information; experimental part
p. 3335 - 3339
(2012/01/19)
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- An efficient and mild CuI/L-proline-catalyzed arylation of acetylacetone or ethyl cyanoacetate
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The coupling reaction of aryl iodides with acetylacetone or ethyl cyanoacetate under catalysis of CuI/L-proline works at relatively mild conditions to provide 3-aryl-2, 4-pentanediones and α-aryl cyanoacetates in moderate to good yields. Georg Thieme Verlag Stuttgart.
- Jiang, Yongwen,Wu, Nan,Wu, Haihong,He, Mingyuan
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p. 2731 - 2734
(2007/10/03)
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- A very reliable method for determination of absolute configuration of chiral secondary alcohols by 1H NMR spectroscopy
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(Chemical equation presented) Surprisingly stable synperiplanar conformers of CFTA esters have led us to develop a new and very reliable method for assigning absolute configurations of even secondary alcohols having minimal structural differences, such as chiral benzhydrols and α-monodeuterated benzyl alcohols.
- Takeuchi, Yoshio,Fujisawa, Hidehito,Noyori, Ryoji
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p. 4607 - 4610
(2007/10/03)
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- A General Method for the Direct α-Arylation of Nitriles with Aryl Chlorides
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The long-standing challenge of developing a general method for the title methodology is met for a broad range of aryl chlorides through the use of bicyclic P(iBuNCH2CH2)3N (1) as a bulky electron-rich ligand for palladium (see scheme, dba = dibenzylideneacetone).
- You, Jingsong,Verkade, John G.
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p. 5051 - 5053
(2007/10/03)
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- P(i-BuNCH2CH2)3N: An efficient ligand for the direct α-arylation of nitriles with aryl bromides
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A new catalyst system for the synthesis of α-aryl-substituted nitriles is reported. The bicyclic triaminophosphine P(i-BuNCH 2CH2)3N (1b) serves as an efficient and versatile ligand for the palladium-catalyzed direct α-arylation of nitriles with aryl bromides. Using ligand 1b, ethyl cyanoacetate and primary as well as secondary nitriles are efficiently coupled with a wide variety of aryl bromides possessing electron-rich, electron-poor, electron-neutral, and sterically hindered groups.
- You, Jingsong,Verkade, John G.
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p. 8003 - 8007
(2007/10/03)
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- A convenient and efficient palladium-catalyzed system for cross-coupling of aryl bromides with active methylene compounds
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A simply catalytic system containing palladium-phosphine complex, generated in situ from PdCl2/tert-phosphino ligand in pyridine, has been systematically studied in the cross-coupling of bromobenzene with malononitrile or ethyl cyanoacetate anion. The effect of molar ratio of phosphine ligand to PdCl2 on the activity of the coupling was also discussed. It is found that the catalytic system has highly catalytic activity to produce aryl malononitriles and cyanoacetates in considerable yields (67-90%) when the substituted aryl bromides were used as substrates.
- Gao, Chengwei,Tao, Xiaochun,Qian, Yanlong,Huang, Jiling
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p. 1716 - 1718
(2007/10/03)
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- A Convenient Synthesis of Some Arylated Phenylsulfonylacetonitriles and Ethyl Cyanoacetates Using Organo-iron Complexes
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A general method for the synthesis of some arylated phenylsulfonylacetonitriles 6a-g, 10a, b and 16 and ethyl cyanoacetates 7a-d and 11a, b is described.Nucleophilic substitution of the cyclopentadienyliron complexes of chloroarenes 1a-g with phenylsulphonylacetonitrile 2 or ethyl cyanoacetate 3 in the presence of potassium carbonate in DMF, at room temperature under a nitrogen atmosphere gave cyclopentadienyliron complexes of arylated phenylsulphonylacetonitriles 4a-g, 8a, b and 15 and ethyl cyanoacetates 5a-d and 9a, b in very good yields (71-94percent).Photolysis of these complexes liberated the arenes (70-91percent).To demonstrate the versatility of this methodological approach, reactions of both carbon nucleophiles 2, 3 with dimethyl chlorobenzene complexes 1h, j gave the desired products 8a, 9a, 12 and 13 without significant steric effect.This synthesis is advantageous over all those previously reported and should be a practical route to a variety of alkanoic acid and heterocyclic precursors.
- Abd-El-Aziz, Alaa S.,Denus, Christine R. de
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p. 293 - 298
(2007/10/02)
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- A SIMPLE ONE-POT CONVERSION OF ARYL HALIDES INTO ARYLACETONITRILES
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When heated in hexamethylphosphoric triamide in the presence of copper(I) iodide, aryl iodides and bromides react with cyanoacetate anion to form arylcyanoacetates, which lose the ester group on hydrolysis, giving the corresponding arylacetonitriles in good to moderate yields.
- Suzuki, Hitomi,Kobayashi, Tsutomu,Yoshida, Yoshiki,Osuka, Atsuhiro
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p. 193 - 194
(2007/10/02)
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- Ester derivatives of pulvinic acid
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Pharmaceutical compositions having anti-arthritic activity comprising an ester derivative of pulvinic acid and methods of producing anti-arthritic activity by administering internally said compositions. Certain of the pulvinic acid derivatives are novel compounds per se.
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