42882-26-8

Upstream product

• 96-31-1 N,N'-Dimethylurea 
• 98-86-2 acetophenone 
• 74-89-5 methylamine 
• 86921-62-2 acetone oxime methanesulfonate 
• 64-17-5 ethanol 
• 19131-99-8 N-methyl-N-[(S)-1-phenylethyl]amine 
• 616-38-6 carbonic acid dimethyl ester 
• 618-36-0 rac-methylbenzylamine 
• 10557-02-5 N-methyl-(1-phenylethylidene)amine 
• 21872-32-2 1-phenylethyl isocyanide 
• 585-71-7 (1-bromoethyl)benzne 
• 67-56-1 methanol 
• 32366-25-9 1-azidoethylbenzene 
• 6948-01-2 N-formyl-(-)-α-phenylethylamine 

Downstream Products

• 10419-51-9 N-benzyl-N-α-phenylethyl-p-toluidine 
• 93161-95-6 (+/-)-2--propionsaeure-diaethylamid 
• 133302-66-6 N-methyl-N-(trimethylsilylmethyl)-α-methylbenzylamine 
• 78222-61-4 N-Methyl-N-(1-phenylethyl)-α-<1-(9-anthryl)-2,2,2-trifluoroethoxy>acetamide 
• 137074-96-5 (4-{2-[Methyl-(1-phenyl-ethyl)-amino]-acetyl}-piperazin-1-yl)-pyridin-3-yl-acetonitrile 
• 68690-89-1 N-nitroso-N-(1-phenylethyl)methylamine 
• 6037-42-9 N-Acryloyl-N-methyl-α-phenylethylamine 
• 87258-81-9 (R,S)-N-methyl-N-(1-phenylethyl)-N-(α-phenylphenacyl)amine 
• 179805-63-1 4-Methoxy-5-[methyl-(1-phenyl-ethyl)-amino]-[1,2]benzoquinone 

Relevant academic research and scientific papers

Single-Site Cobalt Catalysts at New Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Nitroarenes, Nitriles, and Isocyanides

We report here the synthesis of a robust and porous metal-organic framework (MOF), Zr12-TPDC, constructed from triphenyldicarboxylic acid (H2TPDC) and an unprecedented Zr12 secondary building unit (SBU): Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6. The Zr12-SBU can be viewed as an inorganic node dimerized from two commonly observed Zr6 clusters via six μ2-OH groups. The metalation of Zr12-TPDC SBUs with CoCl2 followed by treatment with NaBEt3H afforded a highly active and reusable solid Zr12-TPDC-Co catalyst for the hydrogenation of nitroarenes, nitriles, and isocyanides to corresponding amines with excellent activity and selectivity. This work highlights the opportunity in designing novel MOF-supported single-site solid catalysts by tuning the electronic and steric properties of the SBUs.

Deactivation mechanisms of iodo-iridium catalysts in chiral amine racemization

The homogenous, [IrCp?I2]2, SCRAM catalyst (1) is active in the racemization of chiral amines. NMR, kinetic and structural mechanistic studies have determined the cause of catalyst deactivation to occur when ammonia or methylamine are liberated by hydrolysis or aminolysis of the intermediate imine, which tightly coordinate to the iridium centre to block turnover. Control of moisture and substrate concentration can suppress deactivation, whilst partial reactivation of spent catalyst was identified using hydroiodic acid.

Continuous Flow Chiral Amine Racemization Applied to Continuously Recirculating Dynamic Diastereomeric Crystallizations

A new, dynamic diastereomeric crystallization method has been developed, in which the mother liquors are continuously separated, racemized over a fixed-bed catalyst, and recirculated to the crystallizer in a resolution-racemization-recycle (R3) process. S

Oxidation Under Reductive Conditions: From Benzylic Ethers to Acetals with Perfect Atom-Economy by Titanocene(III) Catalysis

Described here is a titanocene-catalyzed reaction for the synthesis of acetals and hemiaminals from benzylic ethers and benzylic amines, respectively, with pendant epoxides. The reaction proceeds by catalysis in single-electron steps. The oxidative addition comprises an epoxide opening. An H-atom transfer, to generate a benzylic radical, serves as a radical translocation step, and an organometallic oxygen rebound as a reductive elimination. The reaction mechanism was studied by high-level dispersion corrected hybrid functional DFT with implicit solvation. The low-energy conformational space was searched by the efficient CREST program. The stereoselectivity was deduced from the lowest lying benzylic radical structures and their conformations are controlled by hyperconjugative interactions and steric interactions between the titanocene catalyst and the aryl groups of the substrate. An interesting mechanistic aspect is that the oxidation of the benzylic center occurs under reducing conditions.

CHIRALITY SENSING WITH MOLECULAR CLICK CHEMISTRY PROBES

The present invention relates to an analytical method that includes providing a sample potentially containing a chiral analyte that can exist in stereoisomeric forms, and providing a probe selected from the group consisting of coumarin-derived Michael acceptors, dinitrofluoroarenes and analogs thereof, arylsulfonyl chlorides and analogs thereof, arylchlorophosphines and analogs thereof, aryl halophosphites, and halodiazaphosphites. The sample is contacted with the probe under conditions to permit covalent binding of the probe to the analyte, if present in the sample; and, based on any binding that occurs, the absolute configuration of the analyte in the sample, and/or the concentration of the analyte in the sample, and/or the enantiomeric composition of the analyte in the sample is/are determined. The probe may be a coumarin-derived Michael acceptor, a di nitrofluoroarene or analog thereof, an arylsulfonyl chloride or analog thereof, an arylchlorophosphine or analog thereof, an aryl halophosphite, or a halodiazaphosphite.

Tackling N-Alkyl Imines with 3d Metal Catalysis: Highly Enantioselective Iron-Catalyzed Synthesis of α-Chiral Amines

A readily activated iron alkyl precatalyst effectively catalyzes the highly enantioselective hydroboration of N-alkyl imines. Employing a chiral bis(oxazolinylmethylidene)isoindoline pincer ligand, the asymmetric reduction of various acyclic N-alkyl imines provided the corresponding α-chiral amines in excellent yields and with up to >99 % ee. The applicability of this base metal catalytic system was further demonstrated with the synthesis of the pharmaceuticals Fendiline and Tecalcet.

Electrochemical, Iodine-Mediated α-CH Amination of Ketones by Umpolung of Silyl Enol Ethers

The electrochemical, oxidative Umpolung reaction of silyl enol ethers utilizing simple iodide salts for the synthesis of α-amino ketones is described. The products were isolated in excellent yields of up to 100percent, and various functionalized starting materials were accepted in an undivided electrochemical cell design. Moreover, a sensitivity assessment to ensure an improved reproducibility of the reaction and cyclic voltammetry experiments were performed to postulate a plausible reaction mechanism on their basis.

Selective synthesis of mono- and di-methylated amines using methanol and sodium azide as C1 and N1 sources

A Ru(ii) complex mediated synthesis of various N,N-dimethyl and N-monomethyl amines from organic azides using methanol as a methylating agent is reported. This methodology was successfully applied for a one-pot reaction of bromide derivatives and sodium azide in methanol. Notably, by controlling the reaction time several N-monomethylated and N,N-dimethylated amines were synthesized selectively. The practical applicability of this tandem process was revealed by preparative scale reactions with different organic azides and synthesis of an anti-vertigo drug betahistine. Several kinetic experiments and DFT studies were carried out to understand the mechanism of this transformation.

Photometric Characterization of the Reductive Amination Scope of the Imine Reductases from Streptomyces tsukubaensis and Streptomyces ipomoeae

Imine reductases (IREDs) have emerged as promising enzymes for the asymmetric synthesis of secondary and tertiary amines starting from carbonyl substrates. Screening the substrate specificity of the reductive amination reaction is usually performed by time-consuming GC analytics. We found two highly active IREDs in our enzyme collection, IR-20 from Streptomyces tsukubaensis and IR-Sip from Streptomyces ipomoeae, that allowed a comprehensive substrate screening with a photometric NADPH assay. We screened 39 carbonyl substrates combined with 17 amines as nucleophiles. Activity data from 663 combinations provided a clear picture about substrate specificity and capabilities in the reductive amination of these enzymes. Besides aliphatic aldehydes, the IREDs accepted various cyclic (C4–C8) and acyclic ketones, preferentially with methylamine. IR-Sip also accepted a range of primary and secondary amines as nucleophiles. In biocatalytic reactions, IR-Sip converted (R)-3-methylcyclohexanone with dimethylamine or pyrrolidine with high diastereoselectivity (>94–96 % de). The nucleophile acceptor spectrum depended on the carbonyl substrate employed. The conversion of well-accepted substrates could also be detected if crude lysates were employed as the enzyme source.

Asymmetric Reductive Amination of Ketones Catalyzed by Imine Reductases

Biocatalysis employing imine reductases is a promising approach for the one-step generation of chiral amines from ketones. The enzymes reported for this process suffer from low activity and moderate stereoselectivity. We identified a set of enzymes that facilitate this reaction with high to quantitative conversions from a library of 28 imine reductases. This enabled the conversion of ketones with ammonia, methylamine, or butylamine into the corresponding amines. Most importantly, we performed preparative (>100 mg) scale syntheses of amines such as (1S,3R)-N,3-dimethylcyclohexylamine and (R)-N-methyl-2-aminohexane with excellent stereochemical purities (98 % de, 96 % ee) in good yields.