33966-50-6Relevant articles and documents
Rapid and Quantitative Profiling of Substrate Specificity of ω-Transaminases for Ketones
Han, Sang-Woo,Shin, Jong-Shik
, p. 3287 - 3295 (2019/06/21)
ω-Transaminases (ω-TAs) have gained growing attention owing to their capability for asymmetric synthesis of chiral amines from ketones. Reliable high-throughput activity assay of ω-TAs is essential in carrying out extensive substrate profiling and establishing a robust screening platform. Here we report spectrophotometric and colorimetric methods enabling rapid quantitation of ω-TA activities toward ketones in a 96-well microplate format. The assay methods employ benzylamine, a reactive amino donor for ω-TAs, as a cosubstrate and exploit aldehyde dehydrogenase (ALDH) as a reporter enzyme, leading to formation of benzaldehyde detectable by ALDH owing to concomitant NADH generation. Spectrophotometric substrate profiling of two wild-type ω-TAs of opposite stereoselectivity was carried out at 340 nm with 22 ketones, revealing subtle differences in substrate specificities that were consistent with docking simulation results obtained with cognate amines. Colorimetric readout for naked eye detection of the ω-TA activity was also demonstrated by supplementing the assay mixture with color-developing reagents whose color reaction could be quantified at 580 nm. The colorimetric assay was applied to substrate profiling of an engineered ω-TA for 24 ketones, leading to rapid identification of reactive ketones. The ALDH-based assay is expected to be promising for high-throughput screening of enzyme collections and mutant libraries to fish out the best ω-TA candidate as well as to tailor enzyme properties for efficient amination of a target ketone.
An improved and one-pot procedure to the synthesis of symmetric amines by domino reactions of 5-methyl-1,3,4-thiadiazole-2-amine, a new nitrogen atom donor, and alkyl halides
Soleiman-Beigi, Mohammad,Mohammadi, Fariba
, p. 2123 - 2128 (2017/10/26)
Abstract: A new one-pot method has been introduced in this work for the synthesis of symmetrical primary, secondary, and tertiary alkyl amines from alkyl halides and 5-methyl-1,3,4-thiadiazole-2-amine as a nitrogen-transfer reagent. In this method, all three types of amines have been successfully prepared after changing the ratio of substrates and base control. In addition to the introduction of a new nitrogen-transfer reagent, other important features of this work include normal atmospheric conditions and excellent yields under mild reaction conditions.
Method for producing amines by homogeneously catalyzed reductive amination of carbonyl compounds
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Page/Page column 10, (2010/02/11)
The invention relates to the preparation of chiral or achiral amines by reaction of aldehydes or ketones with ammonia or primary or secondary amines in the presence of hydrogen and in the presence of homogeneous metal catalysts under mild conditions. Metal catalysts which can be used are complexes of late transition metals with chiral or achiral phosphorus-containing ligands.
Selective catalytic hydrogenation of organic compounds in supercritical fluids as a continuous process
Hitzler, Martin G.
, p. 137 - 146 (2013/09/08)
We report a new method for continuous hydrogenation in supercritical fluids (CO2 or propane) using heterogeneous noble metal catalysts on Deloxan aminopolysiloxane supports. The method has considerable promise both for laboratory-scale hydrogenation and for the industrial production of fine chemicals. It can be applied to a wide range of organic compounds including alkenes, alkynes, aliphatic and aromatic ketones and aldehydes, epoxides, phenols, oximes, nitrobenzenes, Schiff bases, and nitriles. Conversion of starting materials, product selectivity, and space-time yields of the catalyst are all high, and the reactors themselves are very small (5- and 10-mL volume). Supercritical hydrogenation enables the reaction parameters to be controlled very precisely. Results are presented for a series of different reactions showing product distributions, which are dependent on temperature, pressure, H2 concentration, and the loading and nature of the catalyst. The hydrogenation of cyclohexene has been studied in some detail, and our results are related to the phase diagrams of the ternary system cyclohexane + CO2 + H2, which we present in a novel way, more suited to continuous reactors. Finally, we report that the supercritical hydrogenation of isophorone has advantages over conventional methods.
Amination of butenes over protonic zeolites
Lequitte,Figueras,Moreau,Hub
, p. 255 - 261 (2007/10/03)
The reaction of 1-butene and isobutene with ammonia has been investigated, far from thermodynamic equilibrium, in the pressure range 1-6 MPa over a series of acidic zeolites. The kinetics are compatible with a Langmuir-Hinshelwood mechanism involving adsorbed species. The rates of amination increase with the Si/Al ratio of the solid. A small influence of the zeolite structure is noticed on the relative adsorption coefficients in the case of 1-butene but not in that of isobutene. The catalytic activity calculated per proton is higher on MFI than on BEA or HY zeolites, but this effect of the structure is less than an order of magnitude. Under the conditions of reaction used in this work large pore zeolites show a good resistance to deactivation. It is proposed that deactivation is mainly due to the formation of strongly basic polyalkylamines and not to coke.
Electrophilic Amination of Higher Order Cuprates with N,O-Bis(trimethylsilyl)hydroxylamine
Casarini, Antonella,Dembech, Pasquale,Lazzari, Dario,Marini, Elisabetta,Reginato, Gianna,et al.
, p. 5620 - 5623 (2007/10/02)
In the reaction of higher order cyanocuprates with N,O-bis(trimethylsilyl)hydroxylamine delivery of the NHSiMe3 moiety to one of the anionic ligands in the cuprate takes place even in the absence of external bases according to an "electrophilic amination" protocol.Details of the methodology are given, and the reaction mechanism is analyzed in terms of interception by a mixed bis-metal cluster of a lithium N-silyl-N-siloxyamide, followed by intramolecular C-N coupling.This method is applicable to cyanocuprates bearing aromatic, heteroaromatic, and saturated aliphatic ligands.A number of 2-amino-substituted heterocycles, not easily accesible by normal routes, can be obtained with the aid of a stabilizing silylation at the nitrogen atom.
