- Kinetics and mechanism for oxime formation from methyl pyruvate
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Rate and equilibrium constants for methyl pyruvate oxime formation were determined as a function of pH over the range 0-7 in aqueous solution at 30°C and ionic strength 0.5 by spectrophotometric methods. The reaction occurs with rate-determining carbinolamine dehydration over the entire range of pH investigated. Carbinolamine dehydration is not susceptible to detectable general acid-base catalysis by a carboxylic acid buffer or hydroxylamine/hydroxylammonium ion buffer. Specific acid catalysis for carbinolamine formation is dominant at pH values below 5. Above that value, a pH-independent, water-catalyzed reaction becomes apparent. The pH-independent carbinolamine dehydration is unusually important with this substrate. Copyright
- Cordova,Peraza,Calzadilla,Malpica
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Read Online
- The ruthenium-catalyzed C-H functionalization of enamides with isocyanates: Easy entry to pyrimidin-4-ones
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Ruthenium-catalyzed heteroannulation between enamides and isocyanates has been realized as a complementary approach to conventional strategies for the synthesis of pyrimidin-4-ones. High step-A nd atom-economy was achieved for the rapid construction of such privileged scaffolds, which are found in a multitude of pharmaceutical compounds. The generality and practicability of this transformation were reflected by the broad scope of substrates with diverse functional groups, large-scale synthesis, and late-stage diversification.
- Shi, Pengfei,Li, Song,Hu, Lu-Min,Wang, Cong,Loh, Teck-Peng,Hu, Xu-Hong
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supporting information
p. 11115 - 11118
(2019/09/20)
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- Microwave-promoted one-pot conversion of alcohols to oximes using 1-methylimidazolium nitrate, [Hmim][NO3], as a green promoter and medium
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A wide variety of oximes were prepared from different types of alcohols with hydroxylamine hydrochloride using 1-methylimidaziloum nitrate, [Hmim][NO3], ionic liquid as a reaction medium and promoter under microwave irradiation. This protocol provides a one-pot oxime synthesis with high yields that is facile, eco-friendly and the ionic liquid can be recovered and reused.
- Mirjafari, Arsalan,Mobarrez, Niloufar,O'Brien, Richard A.,Davis Jr, James H.,Noei, Jalil
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experimental part
p. 1065 - 1070
(2012/03/11)
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- Ruthenium-catalyzed hydrovinylation of N-acetylenamines leading to amines with a quaternary carbon center
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A catalytic hydrovinylation of N-acetylenamines with ethylene is reported. This new hydrovinylation reaction is catalyzed by a ruthenium hydride complex, RuHCl(CO)(PCy3)2, providing a series of N-acetylamines with a quaternary carbon center with up to 99% yield.
- Wang, Qiu-Shi,Xie, Jian-Hua,Li, Wei,Zhu, Shou-Fei,Wang, Li-Xin,Zhou, Qi-Lin
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supporting information; scheme or table
p. 3388 - 3391
(2011/08/21)
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- O-TBS-N-tosylhydroxylamine: A reagent for facile conversion of alcohols to oximes
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(Chemical Equation Presented) A variety of oximes were synthesized from the corresponding alcohols, alkyl halides, or alkyl sulfonates without using external oxidants. With this simple two-step procedure involving substitution with readily available TsNHOTBS and subsequent treatment with CsF, a range of oximes were prepared including the ones hardly preparable with conventional procedures.
- Kitahara, Katsushi,Toma, Tatsuya,Shimokawa, Jun,Fukuyama, Tohru
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supporting information; experimental part
p. 2259 - 2261
(2009/05/26)
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- Preparation of α,α-disubstituted α-amino acid derivatives via alkyl addition to α-oxime esters with organozinc species
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An α-oxime ester derivative prepared via treatment of an acetylenedicarboxylate or an α-keto ester with hydroxylamine underwent C-alkylation to the C=N bond of the oxime group by a Lewis-acid-promoted reaction with a trialkylzincate or a dialkylzinc reagent. The O-N bond of the thus obtained adduct was reductively cleaved under hydrogenolysis in the presence of the Pd-C catalyst to afford an α-amino ester. Treatment of the oxime derivative prepared from methyl 5-bromo-2-oxopentanoate with the trialkylzincate gave an α-alkyl proline derivative via the addition reaction followed by the intramolecular attack upon a bromine-bearing carbon. The reaction of ethyl 4-oxo-2-pentynoate with hydroxylamine formed an isoxazole derivative by way of the intramolecular attack of an in situ-generated oxime to the carbonyl group. From this isoxazole derivative, ethyl 2-amino-4-oxo-2- pentenoate was given by the Pd-C-catalyzed hydrogenolysis. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Mitani, Michiharu,Tanaka, Yasunori,Sawada, Akihiko,Misu, Ayuko,Matsumoto, Yoshihiro
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experimental part
p. 1383 - 1391
(2009/04/04)
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- Indium mediated allylation of glyoxylate oxime ethers, esters and cyanoformates
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An indium mediated procedure has been developed for the allylation of activated O-functionalised oximes and nitriles as exemplified by a variety of glyoxylate derivatives. This method gives the corresponding free (or protected) amine in a one pot-process. The method is regiospecific and is carried out under remarkably mild conditions so that even oxime esters can be subjected to the typical reaction conditions.
- Ritson, Dougal J.,Cox, Russell J.,Berge, John
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p. 1921 - 1933
(2007/10/03)
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- Metal-oxime chelates for use as radiopharmaceutical agents
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Novel metal chelating compounds, and radiometal, e.g., technetium-99m complexes thereof. The compounds can be used to radiolabel small biologically active species with minimal effect on their biodistribution and activity. The compounds have formula (a) or (b): STR1 where Z is (CR2)n or (CR)n, n is 2 or 3, X is a ligand comprising S, N or O, each R is H or C1-C20 substituted or unsubstituted hydrocarbon group, provided that 1-3 CR2 groups represent a CO (amide) moiety, and provided that 1-3 R may each comprise a targeting group and/or a protein reactive functionality.
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- Synthesis of 1-acylamino-1-(trimethylsiloxy)alkanes by trimethylsilyl trifluoromethanesulfonate-catalysed addition of bis(trimethylsilyl)amides to aldehydes
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Bis(trimethylsilyl)formamide reacts with aldehydes in refluxing chloroform, or at room temperature with catalysis by trimethylsilyl trifluoromethanesulfonate, to give 1-acylamino-1-(trimethylsiloxy)alkanes; similar results are obtained with other bis(trimethylsilyl)amides, but surprisingly not with bis(trimethylsilyl)acetamide, and addition of bis(trimethylsilyl)formamide to ketones and acetals can also be accomplished using TMS triflate as catalyst.
- Johnson, A. Peter,Luke, Richard W. A.,Steele, Robert W.,Boa, Andrew N.
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p. 883 - 893
(2007/10/03)
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- Substituted phenylphosphinyloxy- and phosphinylthio-iminocarboxylates useful for the control of weeds
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Novel substituted phenylphosphinyloxy- and phenylphosphinylthio-iminocarboxylates, synthesis thereof, intermediates therefor, and the use of said novel compounds for the control of weeds.
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