3886-69-9Relevant articles and documents
Synthesis and reactivity towards carbon monoxide of an optically active endo five-membered ortho-cyclopalladated imine: X-ray molecular structure of trans-(μ-Cl)2[Pd(κ2-C,N-(R)-C6H4-CH{double bond, long}N-CHMe-Ph)]2
Albert, Joan,D'Andrea, Luci?a,Granell, Jaume,Tavera, Raquel,Font-Bardia, Mercè,Solans, Xavier
, p. 3070 - 3080 (2007)
(R)-1-Phenylethyl-benzylidene-amine (1) reacted with Pd(OAc)2 in acetic acid at 60 °C under nitrogen affording the acetato-bridged dinuclear endo five-membered ortho-cyclopalladated compound (μ-OAc)2[Pd(κ2-C,N-(R)-C6H4-CH{double bond, long}N-CHMe-Ph)]2 (2) in 65% yield. Compound 2 was converted by a metathesis reaction with LiCl into the corresponding chloro-bridged dinuclear cyclopalladated compound (μ-Cl)2[Pd(κ2-C,N-(R)-C6H4-CH{double bond, long}N-CHMe-Ph)]2 (3). 1H NMR of CDCl3 solutions of compounds 2 and 3 treated separately with py-d5, (R)-1-phenylethylamine and racemic 1-phenylethylamine were consistent with the endo cyclopalladated structure and the R absolute configuration of the chiral carbon atoms of compounds 2 and 3. Compounds 2 and 3 reacted with carbon monoxide in methanol affording, as major compounds, methyl 2-formylbenzoate (91% chemical yield) and the epimers of 3-methoxy-2-[(R)-1-phenylethyl]isoindolin-1-one (64% chemical yield) in ca. 20% diastereomeric excess, respectively. The trans isomer of compound 3 crystallized in the P21 monoclinic space group with a = 10.430(4) A?, b = 12.082(8) A?, c = 11.168(4) A? and β = 95.20(3)° and presented C-H?Cl intramolecular and C-H?Pd intermolecular non-conventional hydrogen bonds.
Determination of absolute configurations of amines and amino acids using nonchiral derivatizing agents (NCDA) and deuterium NMR.
Chalard,Bertrand,Canet,Thery,Remuson,Jeminet
, p. 2431 - 2434 (2000)
Enantiomeric analysis and empirical determination of the absolute configuration of amines and amino acids can be easily performed using acetyl-d(3) chloride as a nonchiral derivatizing agent (deuterium probe) and deuterium NMR in a chiral solvent (Courtieu's method). In the case of amino acids, derivatization to amido esters, performed with methanol-d(4) and acetyl-d(3) chloride, gives a double opportunity for enantiomeric analysis.
Method for recycling perindopril intermediate resolving agent (R)-(+)-alpha-phenylethylamine
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Paragraph 0049-0052, (2021/07/10)
The invention discloses a method for recycling and reusing a perindopril intermediate resolving agent (R)-(+)-alpha-phenylethylamine. The method comprises the following steps: S1, heating the free mother liquor to 30-45 DEG C, dropwise adding inorganic alkali to adjust the pH to be alkaline, adding an organic solvent A to extract twice, combining organic layers, controlling the temperature to be less than or equal to 50 DEG C for desolventizing under reduced pressure, and re-dissolving the distilled mother liquor in an organic solvent B; s2, cooling the distillation mother liquor to be less than or equal to 10 DEG C, dropwise adding inorganic acid to adjust the pH to be alkalescent, crystallizing, carrying out suction filtration, and filtering and washing with an organic solvent B to obtain a wet product; s3, dissolving the wet product in drinking water, heating the product to 30-45 DEG C, dropwise adding inorganic alkali to adjust the pH to be alkaline, and adding an organic solvent A for extraction. The method is different from a conventional chiral amine recovery method of alkaline extraction and reduced evaporation, an improved method of alkaline extraction, desolvation, acid crystallization, alkaline extraction and reduced evaporation is adopted, the process stability is high, and the obtained recovered (R)-(+)-alpha-phenylethylamine is colorless and transparent in appearance, high in purity, good in application effect and large in cycle index.
Generation of Oxidoreductases with Dual Alcohol Dehydrogenase and Amine Dehydrogenase Activity
Tseliou, Vasilis,Schilder, Don,Masman, Marcelo F.,Knaus, Tanja,Mutti, Francesco G.
supporting information, p. 3315 - 3325 (2020/12/11)
The l-lysine-?-dehydrogenase (LysEDH) from Geobacillus stearothermophilus naturally catalyzes the oxidative deamination of the ?-amino group of l-lysine. We previously engineered this enzyme to create amine dehydrogenase (AmDH) variants that possess a new hydrophobic cavity in their active site such that aromatic ketones can bind and be converted into α-chiral amines with excellent enantioselectivity. We also recently observed that LysEDH was capable of reducing aromatic aldehydes into primary alcohols. Herein, we harnessed the promiscuous alcohol dehydrogenase (ADH) activity of LysEDH to create new variants that exhibited enhanced catalytic activity for the reduction of substituted benzaldehydes and arylaliphatic aldehydes to primary alcohols. Notably, these novel engineered dehydrogenases also catalyzed the reductive amination of a variety of aldehydes and ketones with excellent enantioselectivity, thus exhibiting a dual AmDH/ADH activity. We envisioned that the catalytic bi-functionality of these enzymes could be applied for the direct conversion of alcohols into amines. As a proof-of-principle, we performed an unprecedented one-pot “hydrogen-borrowing” cascade to convert benzyl alcohol to benzylamine using a single enzyme. Conducting the same biocatalytic cascade in the presence of cofactor recycling enzymes (i.e., NADH-oxidase and formate dehydrogenase) increased the reaction yields. In summary, this work provides the first examples of enzymes showing “alcohol aminase” activity.