- Catalytic asymmetric oxidative carbonylation-induced kinetic resolution of sterically hindered benzylamines to chiral isoindolinones
-
A highly enantioselective kinetic resolution of sterically hindered benzylamines has been achieved for the first time through transition-metal-catalyzed oxidative carbonylation, in which the new KR strategy offered a new approach to afford chiral isoindolinones (er up to 97?:?3) and the origin of chemoselectivity and stereoselectivity was confirmed by density functional theory (DFT) calculations.
- Mu, Qiu-Qi,Nie, Yi-Xue,Li, Hang,Bai, Xing-Feng,Liu, Xue-Wei,Xu, Zheng,Xu, Li-Wen
-
supporting information
p. 1778 - 1781
(2021/02/27)
-
- 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.
- Funk, Pierre,Richrath, Ruben B.,Bohle, Fabian,Grimme, Stefan,Gans?uer, Andreas
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p. 5482 - 5488
(2021/02/03)
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- Iterative Alanine Scanning Mutagenesis Confers Aromatic Ketone Specificity and Activity of L-Amine Dehydrogenases
-
Direct reductive amination of prochiral ketones catalyzed by amine dehydrogenases is attractive in the synthesis of active pharmaceutical ingredients. Here, we report the protein engineering of L-Bacillus cereus amine dehydrogenase to allow reactivity on synthetically useful aromatic ketone substrates using an iterative, multiple-site alanine scanning mutagenesis approach. Mutagenesis libraries based on molecular docking, iterative alanine scanning, and double-proximity filter approach significantly expand the scope of active pharmaceutical ingredients relevant building blocks. The eventual quintuple mutant (A115G/T136A/L42A/V296A/V293A) showed reactivity toward aromatic ketones 12 a (5-phenyl-pentan-2-one) and 13 a (6-phenyl-hexan-2-one), which have not been reported to serve as targets of reductive amination by currently available amine dehydrogenases. Docking simulation and tunnel analysis provided valuable insights into the source of the acquired specificity and activity.
- Mu, Xiaoqing,Wu, Tao,Mao, Yong,Zhao, Yilei,Xu, Yan,Nie, Yao
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p. 5243 - 5253
(2021/11/16)
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- Method for preparing primary amine by catalyzing reductive amination of aldehyde ketone compounds
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The invention discloses a method for preparing primary amine by catalyzing reductive amination of aldehyde ketone compounds. The method comprises the following steps: 1) mixing nickel nitrate hexahydrate, citric acid and an organic solvent, carrying out heating and stirring until a colloidal material is obtained, drying the colloidal material, roasting the colloidal material in a protective atmosphere, pickling, washing and drying a roasted product, and performing a partial oxidation reaction on a dried product in an oxygen-nitrogen mixed atmosphere to obtain a catalyst for a reductive amination reaction; and 2) mixing aldehyde or ketone compounds, a methanol solution of ammonia and the reductive amination reaction catalyst, introducing hydrogen, and carrying out a reductive amination reaction. The method has the advantages of high primary amine yield, high selectivity, wide aldehyde ketone substrate range, short reaction time, mild reaction conditions, low cost, greenness, economicalperformance and the like; the used reductive amination reaction catalyst can be recycled more than 10 times, and the catalytic activity of the catalyst is not obviously changed in gram-level reactions; and the method is suitable for large-scale application.
- -
-
Paragraph 0068-0069; 0080-0083
(2020/05/30)
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- Design, synthesis and antifungal activity of threoninamide carbamate derivatives via pharmacophore model
-
Thirty-six novel threoninamide carbamate derivatives were designed and synthesised using active fragment-based pharmacophore model. Antifungal activities of these compounds were tested against Oomycete fungi Phytophthora capsici in vitro and in vivo. Interestingly, compound I-1, I-2, I-3, I-6 and I-7 exhibited moderate control effect (>50%) against Pseudoperonospora cubensis in greenhouse at 6.25 μg/mL, which is better than that of control. Meanwhile most of these compounds exhibited significant inhibitory against P. capsici. The other nine fungi were also tested. More importantly, some compounds exhibited remarkably high activities against Sclerotinia sclerotiorum, P. piricola and R. solan in vitro with EC50 values of 3.74–9.76 μg/mL. It is possible that the model is reliabile and this method can be used to discover lead compounds for the development of fungicides.
- Dong, Wei-Li,Du, Xiu-Jiang,Liu, Xing-Hai,Peng, Xing-Jie,Zhao, Rui-Qi,Zhao, Wei-Guang
-
p. 682 - 691
(2020/03/19)
-
- Rh(III)-catalyzed synthesis of isoquinolines using the N-Cl bond of N-chloroimines as an internal oxidant
-
The Rh(III)-catalyzed coupling of N-chloroimines with alkynes for the efficient synthesis of isoquinolines is reported. This represents the first use of the N-Cl bond of N-chloroimines as an internal oxidant for construction of the isoquinoline skeleton. The synthesis features atom and step economy, a green solvent (EtOH), mild reaction conditions, and a broad substrate scope.
- Chu, Benfa,Fang, Lili,Guo, Shan,Qi, Bing,Shi, Pengfei,Wang, Qi,Zhu, Jin
-
supporting information
(2020/03/10)
-
- The Synthesis of Primary Amines through Reductive Amination Employing an Iron Catalyst
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The reductive amination of ketones and aldehydes by ammonia is a highly attractive method for the synthesis of primary amines. The use of catalysts, especially reusable catalysts, based on earth-abundant metals is similarly appealing. Here, the iron-catalyzed synthesis of primary amines through reductive amination was realized. A broad scope and a very good tolerance of functional groups were observed. Ketones, including purely aliphatic ones, aryl–alkyl, dialkyl, and heterocyclic, as well as aldehydes could be converted smoothly into their corresponding primary amines. In addition, the amination of pharmaceuticals, bioactive compounds, and natural products was demonstrated. Many functional groups, such as hydroxy, methoxy, dioxol, sulfonyl, and boronate ester substituents, were tolerated. The catalyst is easy to handle, selective, and reusable and ammonia dissolved in water could be employed as the nitrogen source. The key is the use of a specific Fe complex for the catalyst synthesis and an N-doped SiC material as catalyst support.
- B?umler, Christoph,Bauer, Christof,Kempe, Rhett
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p. 3110 - 3114
(2020/06/01)
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- Facile synthesis of controllable graphene-co-shelled reusable Ni/NiO nanoparticles and their application in the synthesis of amines under mild conditions
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The primary objective of many researchers in chemical synthesis is the development of recyclable and easily accessible catalysts. These catalysts should preferably be made from Earth-abundant metals and have the ability to be utilised in the synthesis of pharmaceutically important compounds. Amines are classified as privileged compounds, and are used extensively in the fine and bulk chemical industries, as well as in pharmaceutical and materials research. In many laboratories and in industry, transition metal catalysed reductive amination of carbonyl compounds is performed using predominantly ammonia and H2. However, these reactions usually require precious metal-based catalysts or RANEY nickel, and require harsh reaction conditions and yield low selectivity for the desired products. Herein, we describe a simple and environmentally friendly method for the preparation of thin graphene spheres that encapsulate uniform Ni/NiO nanoalloy catalysts (Ni/NiO?C) using nickel citrate as the precursor. The resulting catalysts are stable and reusable and were successfully used for the synthesis of primary, secondary, tertiary, and N-methylamines (more than 62 examples). The reaction couples easily accessible carbonyl compounds (aldehydes and ketones) with ammonia, amines, and H2 under very mild industrially viable and scalable conditions (80 °C and 1 MPa H2 pressure, 4 h), offering cost-effective access to numerous functionalized, structurally diverse linear and branched benzylic, heterocyclic, and aliphatic amines including drugs and steroid derivatives. We have also demonstrated the scale-up of the heterogeneous amination protocol to gram-scale synthesis. Furthermore, the catalyst can be immobilized on a magnetic stirring bar and be conveniently recycled up to five times without any significant loss of catalytic activity and selectivity for the product.
- Cui, Zhibing,Liu, Jianguo,Liu, Qiying,Ma, Longlong,Singh, Thishana,Wang, Chenguang,Wang, Nan,Zhu, Yuting
-
supporting information
p. 7387 - 7397
(2020/11/19)
-
- Enzymatic Primary Amination of Benzylic and Allylic C(sp3)-H Bonds
-
Aliphatic primary amines are prevalent in natural products, pharmaceuticals, and functional materials. While a plethora of processes are reported for their synthesis, methods that directly install a free amine group into C(sp3)-H bonds remain unprecedented. Here, we report a set of new-to-nature enzymes that catalyze the direct primary amination of C(sp3)-H bonds with excellent chemo-, regio-, and enantioselectivity, using a readily available hydroxylamine derivative as the nitrogen source. Directed evolution of genetically encoded cytochrome P411 enzymes (P450s whose Cys axial ligand to the heme iron has been replaced with Ser) generated variants that selectively functionalize benzylic and allylic C-H bonds, affording a broad scope of enantioenriched primary amines. This biocatalytic process is efficient and selective (up to 3930 TTN and 96percent ee), and can be performed on preparative scale.
- Jia, Zhi-Jun,Gao, Shilong,Arnold, Frances H.
-
supporting information
p. 10279 - 10283
(2020/07/27)
-
- Nano-Fe3O4@SiO2-SO3H: A magnetic, reusable solid-acid catalyst for solvent-free reduction of oximes to amines with the NaBH3CN/ZrCl4 system
-
In this study, the immobilization of sulfonic acid on silica-layered magnetite was carried out by the reaction of ClSO3H with silica-layered magnetite. The prepared magnetic nanoparticles of Fe3O4@SiO2-SO3H were then characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, vibrating sample magnetometry, and transmission electron microscopy. The sulfonated nanocomposite exhibited excellent catalytic activity and reusability in the reduction of various aldoximes and ketoximes with NaBH3CN in the presence of ZrCl4. All reactions were carried out under solvent-free conditions (r.t. or 75–80°C) within 3–70 min to afford amines in high to excellent yields.
- Sadighnia, Leila,Zeynizadeh, Behzad,Karami, Shiva,Abdollahi, Mohammad
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p. 535 - 542
(2019/01/04)
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- Deracemization of Racemic Amines to Enantiopure (R)- and (S)-amines by Biocatalytic Cascade Employing ω-Transaminase and Amine Dehydrogenase
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A one-pot deracemization strategy for α-chiral amines is reported involving an enantioselective deamination to the corresponding ketone followed by a stereoselective amination by enantiocomplementary biocatalysts. Notably, this cascade employing a ω-transaminase and amine dehydrogenase enabled the access to both (R)-and (S)-amine products, just by controlling the directions of the reactions catalyzed by them. A wide range of (R)-and (S)-amines was obtained with excellent conversions (>80 %) and enantiomeric excess (>99 % ee). Finally, preparative scale syntheses led to obtain enantiopure (R)- and (S)-13 with the isolated yields of 53 and 75 %, respectively.
- Yoon, Sanghan,Patil, Mahesh D.,Sarak, Sharad,Jeon, Hyunwoo,Kim, Geon-Hee,Khobragade, Taresh P.,Sung, Sihyong,Yun, Hyungdon
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p. 1898 - 1902
(2019/02/27)
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- Rh(III)-Catalyzed Coupling of N-Chloroimines with α-Diazo-α-phosphonoacetates for the Synthesis of 2 H-Isoindoles
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We report herein the first use of N-chloroimines as effective synthons for directed C-H functionalization. Rh(III)-catalyzed coupling of N-chloroimines with α-diazo-α-phosphonoacetates allows for efficient dechlorinative/dephosphonative access to 2H-isoindoles. Further deesterification under Ni(II) catalysis enables the complete elimination of reactivity-assisting groups and full exposure of reactivity of C3 and N2 ring atoms for attaching structurally distinct appendages.
- Qi, Bing,Li, Lei,Wang, Qi,Zhang, Wenjing,Fang, Lili,Zhu, Jin
-
supporting information
p. 6860 - 6863
(2019/09/12)
-
- Transition-Metal-Free Hydrogen Autotransfer: Diastereoselective N-Alkylation of Amines with Racemic Alcohols
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A practical method for the synthesis of α-chiral amines by alkylation of amines with alcohols in the absence of any transition-metal catalysts has been developed. Under the co-catalysis of a ketone and NaOH, racemic secondary alcohols reacted with Ellman's chiral tert-butanesulfinamide by a hydrogen autotransfer process to afford chiral amines with high diastereoselectivities (up to >99:1). Broad substrate scope and up to a 10 gram scale production of chiral amines were demonstrated. The method was applied to the synthesis of chiral deuterium-labelled amines with high deuterium incorporation and optical purity, including examples of chiral deuterated drugs. The configuration of amine products is found to be determined solely by the configuration of the chiral tert-butanesulfinamide regardless of that of alcohols, and this is corroborated by DFT calculations. Further mechanistic studies showed that the reaction is initiated by the ketone catalyst and involves a transition state similar to that proposed for the Meerwein–Ponndorf–Verley (MPV) reduction, and importantly, it is the interaction of the sodium cation of the base with both the nitrogen and oxygen atoms of the sulfinamide moiety that makes feasible, and determines the diastereoselectivity of, the reaction.
- Xiao, Miao,Yue, Xin,Xu, Ruirui,Tang, Weijun,Xue, Dong,Li, Chaoqun,Lei, Ming,Xiao, Jianliang,Wang, Chao
-
supporting information
p. 10528 - 10536
(2019/07/17)
-
- Method for synthesizing chiral amine compound
-
The present invention provides a method for synthesizing a chiral amine compound. The method comprises the following steps: (1) reacting a compound of formula I with t-butylsulfonamide in the presenceof a catalyst to obtain a compound having a structure represented by formula II; 2) reacting the compound of the formula II in a hydrogen atmosphere in the presence of an iridium catalyst and a ligand to obtain a compound of formula III; and (3) carrying out a t-butylsulfonyl group removal reaction on the compound of the formula III to obtain the chiral amine compound. The method constructs the structure of sulfonamide by a keto carbonylgroup, and synthesizes the chiral amine compound with the aralkylamine structure by an asymmetric catalytic hydrogenation reaction of the sulfonamide structure, the ee value is generally 80% or above, the highest ee value is 99% or above, the yield of each step reaction can reach 90% or above, and the total yield is high.
- -
-
Paragraph 0064; 0071-0073; 0117-0119
(2019/10/01)
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- Rapid and Quantitative Profiling of Substrate Specificity of ω-Transaminases for Ketones
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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.
- Han, Sang-Woo,Shin, Jong-Shik
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p. 3287 - 3295
(2019/06/21)
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- Method for synthesis of (R)-1-(4-methyl phenyl) ethylamine
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The invention discloses a method for synthesis of (R)-1-(4-methyl phenyl) ethylamine. The method includes: subjecting a compound 3 to deacylation to obtain (R)-1-(4-methyl phenyl) ethylamine in a C4-C10 monoalcohol solvent and in the presence of alkali metal hydroxide, wherein R refers to ethanoyl, propionyl or butyryl. The method is low in synthesis cost, simple in step, safe in operation, low inby-products, simple in aftertreatment, easy to purify intermediate products and final products, high in whole yield, high in final product purity and easy in industrialization.
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-
- Mapping the substrate scope of monoamine oxidase (MAO-N) as a synthetic tool for the enantioselective synthesis of chiral amines
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A library of 132 racemic chiral amines (α-substituted methylbenzylamines, benzhydrylamines, 1,2,3,4-tetrahydronaphthylamines (THNs), indanylamines, allylic and homoallylic amines, propargyl amines) was screened against the most versatile monoamine oxidase (MAO-N) variants D5, D9 and D11. MAO-N D9 exhibited the highest activity for most substrates and was applied to the deracemisation of a comprehensive set of selected primary amines. In all cases, excellent enantioselectivity was achieved (e.e. >99%) with moderate to good yields (55–80%). Conditions for the deracemisation of primary amines using a MAO-N/borane system were further optimised using THN as a template addressing substrate load, nature of the enzyme preparation, buffer systems, borane sources, and organic co-solvents.
- Herter, Susanne,Medina, Florian,Wagschal, Simon,Benha?m, Cyril,Leipold, Friedemann,Turner, Nicholas J.
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p. 1338 - 1346
(2017/10/06)
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- N-Alkylation of Aqueous Ammonia with Alcohols Leading to Primary Amines Catalyzed by Water-Soluble N-Heterocyclic Carbene Complexes of Iridium
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A new catalytic system for the N-monoalkylation of aqueous ammonia with a variety of alcohols was developed. Water-soluble dicationic complexes of iridium bearing N-heterocyclic carbene and diammine ligands exhibited high catalytic activity for this type of reaction on the basis of hydrogen-transfer processes without generating harmful or wasteful byproducts. Various primary amines were efficiently synthesized by using safe, inexpensive, and easily handled aqueous ammonia as a nitrogen source. For example, the reaction of 1-(4-methylphenyl)ethanol with aqueous ammonia in the presence of a water-soluble N-heterocyclic carbene complex of iridium at 150 °C for 40 h gave 1-(4-methylphenyl)ethylamine in 83 % yield.
- Fujita, Ken-Ichi,Furukawa, Shohichi,Morishima, Namino,Shimizu, Mineyuki,Yamaguchi, Ryohei
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p. 1993 - 1997
(2018/03/13)
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- Substituent effects on chiral resolutions of derivatized 1-phenylalkylamines by heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin GC stationary phase
-
Chiral resolutions of trifluoroacetyl-derivatized 1-phenylalkylamines with different type and position of substituent were investigated by capillary gas chromatography by using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin diluted in OV-1701 as a chiral stationary phase. The influence of column temperature on retention and enantioselectivity was examined. All enantiomers of meta-substituted analytes as well as fluoro-substituted analytes could be resolved. Temperature had a favorable influence on enantioselectivity for small amines with substituents at the ortho-position. The type of substituent at the stereogenic center of amines also had a crucial effect as the ethyl group led to poor enantioseparation. Among all analytes studied, trifluoroacetyl-derivatized 1-(2′-fluorophenyl)ethylamine exhibited baseline resolution with the shortest analysis time.
- Issaraseriruk, Natthapol,Sritana-anant, Yongsak,Shitangkoon, Aroonsiri
-
supporting information
p. 900 - 906
(2018/05/08)
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- Asymmetric Synthesis of Chiral Primary Amines by Ruthenium-Catalyzed Direct Reductive Amination of Alkyl Aryl Ketones with Ammonium Salts and Molecular H2
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A ruthenium/C3-TunePhos catalytic system has been identified for highly efficient direct reductive amination of simple ketones. The strategy makes use of ammonium acetate as the amine source and H2 as the reductant and is a user-friendly and operatively simple access to industrially relevant primary amines. Excellent enantiocontrol (>90% ee for most cases) was achieved with a wide range of alkyl aryl ketones. The practicability of this methodology has been highlighted by scalable synthesis of key intermediates of three drug molecules. Moreover, an improved synthetic route to the optimal diphosphine ligand C3-TunePhos is also presented.
- Tan, Xuefeng,Gao, Shuang,Zeng, Weijun,Xin, Shan,Yin, Qin,Zhang, Xumu
-
supporting information
p. 2024 - 2027
(2018/02/19)
-
- Evaluation of the Edman degradation product of vancomycin bonded to core-shell particles as a new HPLC chiral stationary phase
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A modified macrocyclic glycopeptide-based chiral stationary phase (CSP), prepared via Edman degradation of vancomycin, was evaluated as a chiral selector for the first time. Its applicability was compared with other macrocyclic glycopeptide-based CSPs: TeicoShell and VancoShell. In addition, another modified macrocyclic glycopeptide-based CSP, NicoShell, was further examined. Initial evaluation was focused on the complementary behavior with these glycopeptides. A screening procedure was used based on previous work for the enantiomeric separation of 50 chiral compounds including amino acids, pesticides, stimulants, and a variety of pharmaceuticals. Fast and efficient chiral separations resulted by using superficially porous (core-shell) particle supports. Overall, the vancomycin Edman degradation product (EDP) resembled TeicoShell with high enantioselectivity for acidic compounds in the polar ionic mode. The simultaneous enantiomeric separation of 5 racemic profens using liquid chromatography-mass spectrometry with EDP was performed in approximately 3?minutes. Other highlights include simultaneous liquid chromatography separations of rac-amphetamine and rac-methamphetamine with VancoShell, rac-pseudoephedrine and rac-ephedrine with NicoShell, and rac-dichlorprop and rac-haloxyfop with TeicoShell.
- Hellinghausen, Garrett,Lopez, Diego A.,Lee, Jauh T.,Wang, Yadi,Weatherly, Choyce A.,Portillo, Abiud E.,Berthod, Alain,Armstrong, Daniel W.
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p. 1067 - 1078
(2018/08/01)
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- METHOD FOR THE HOMOGENEOUS CATALYTIC REDUCTIVE AMINATION OF CARBONYL COMPOUNDS
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The present invention relates to a method for the reductive amination of a carbonyl compound, comprising one or more carbonyl groups amenable to reductive amination, forming the corresponding primary amine, characterized in that the reaction is carried out in the presence of a homogeneously dissolved catalyst complex K, comprising at least one metal atom from Group 8, 9 or 10 of the periodic table, bearing a bidentate phosphane ligand, a carbonyl ligand, a neutral ligand and a hydride ligand, and also an acid as co-catalyst.
- -
-
Paragraph 0212; 0219-0221
(2018/07/29)
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- In vitro biocatalytic pathway design: Orthogonal network for the quantitative and stereospecific amination of alcohols
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The direct and efficient conversion of alcohols into amines is a pivotal transformation in chemistry. Here, we present an artificial, oxidation-reduction, biocatalytic network that employs five enzymes (alcohol dehydrogenase, NADP-oxidase, catalase, amine dehydrogenase and formate dehydrogenase) in two concurrent and orthogonal cycles. The NADP-dependent oxidative cycle converts a diverse range of aromatic and aliphatic alcohol substrates to the carbonyl compound intermediates, whereas the NAD-dependent reductive aminating cycle generates the related amine products with >99% enantiomeric excess (R) and up to >99% conversion. The elevated conversions stem from the favorable thermodynamic equilibrium (K′eq = 1.88 × 1042 and 1.48 × 1041 for the amination of primary and secondary alcohols, respectively). This biocatalytic network possesses elevated atom efficiency, since the reaction buffer (ammonium formate) is both the aminating agent and the source of reducing equivalents. Additionally, only dioxygen is needed, whereas water and carbonate are the by-products. For the oxidative step, we have employed three variants of the NADP-dependent alcohol dehydrogenase from Thermoanaerobacter ethanolicus and we have elucidated the origin of the stereoselective properties of these variants with the aid of in silico computational models.
- Knaus, Tanja,Cariati, Luca,Masman, Marcelo F,Mutti, Francesco G.
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p. 8313 - 8325
(2017/10/19)
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- Asymmetric catalysis of the carbonyl-amine condensation: Kinetic resolution of primary amines
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A Br?nsted acid catalyzed kinetic resolution of primary amines is described that is based on the condensation between an amine and a carbonyl compound. 1,3-Diketones react with racemic α-branched amines to furnish the corresponding enantioenriched enaminone and recovered starting material. Good to excellent enantioselectivity was observed with both aromatic and aliphatic primary amines. This process represents the first small-molecule catalyzed kinetic resolution of aliphatic amines.
- Das, Sayantani,Majumdar, Nilanjana,De, Chandra Kanta,Kundu, Dipti Sankar,Dohring, Arno,Garczynski, Anika,List, Benjamin
-
supporting information
p. 1357 - 1359
(2017/02/10)
-
- Amine dehydrogenases: Efficient biocatalysts for the reductive amination of carbonyl compounds
-
Amines constitute the major targets for the production of a plethora of chemical compounds that have applications in the pharmaceutical, agrochemical and bulk chemical industries. However, the asymmetric synthesis of α-chiral amines with elevated catalytic efficiency and atom economy is still a very challenging synthetic problem. Here, we investigated the biocatalytic reductive amination of carbonyl compounds employing a rising class of enzymes for amine synthesis: amine dehydrogenases (AmDHs). The three AmDHs from this study-operating in tandem with a formate dehydrogenase from Candida boidinii (Cb-FDH) for the recycling of the nicotinamide coenzyme-performed the efficient amination of a range of diverse aromatic and aliphatic ketones and aldehydes with up to quantitative conversion and elevated turnover numbers (TONs). Moreover, the reductive amination of prochiral ketones proceeded with perfect stereoselectivity, always affording the (R)-configured amines with more than 99% enantiomeric excess. The most suitable amine dehydrogenase, the optimised catalyst loading and the required reaction time were determined for each substrate. The biocatalytic reductive amination with this dual-enzyme system (AmDH-Cb-FDH) possesses elevated atom efficiency as it utilizes the ammonium formate buffer as the source of both nitrogen and reducing equivalents. Inorganic carbonate is the sole by-product.
- Knaus, Tanja,B?hmer, Wesley,Mutti, Francesco G.
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p. 453 - 463
(2017/08/14)
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- A su ammonia amide carbamate derivative and application thereof
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The invention belongs to the field of plant bactericide, and relates to a threonyl amine carbamate derivative shown as the general formula (I) and salt capable of being accepted pharmaceutically. Substituent groups R1, R2 and R3 have the definitions given by a specification. The invention further relates to a preparation method of the compound of the general formula (I), a midbody specially developed for preparing the threonyl amine carbamate derivative and an application of the threonyl amine carbamate derivative in plant disease prevention and control. The formula is shown in the specification.
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-
Paragraph 0090; 0102; 0130
(2017/09/02)
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- SYNTHESIS OF AMIDES AND AMINES FROM ALDEHYDES OR KETONES BY HETEROGENEOUS METAL CATALYSIS
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This invention concerns the first mild and efficient synthesis of primary amines and amides from aldehydes or ketones using a heterogeneous metal catalystand amine donor. The initial heterogeneous metal- catalyzed reaction between the carbonyl and the amine donor components is followed up with the addition of a suitable acylating agent component in one-pot. Hence, the present invention provides a novel catalytic one-pot three-component synthesis of amides. Moreover, the integration of enzyme catalysis allows for eco-friendly one-pot co-catalytic synthesis ofamides from aldehyde and ketone substrates, respectively. The process can be applied to the co-catalytic one-pot three-component synthesis of capsaicin and its analogues from vanillin or vanillyl alcohol. It can also be applied for asymmetric synthesis. In the present invention, a novel co-catalytic reductive amination/dynamic kinetic resolution (dkr) relay sequence for the asymmetric synthesis of optically active amides from ketones is disclosed. Moreover, implementation of a catalytic reductive amination/kinetic resolution (kr) relay sequence produces the corresponding optically active amide product and optical active primary amine product with the opposite stereochemistry from the starting ketones.
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Page/Page column 22
(2016/07/05)
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- Integrated Heterogeneous Metal/Enzymatic Multiple Relay Catalysis for Eco-Friendly and Asymmetric Synthesis
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Organic synthesis is in general performed using stepwise transformations where isolation and purification of key intermediates is often required prior to further reactions. Herein we disclose the concept of integrated heterogeneous metal/enzymatic multiple relay catalysis for eco-friendly and asymmetric synthesis of valuable molecules (e.g., amines and amides) in one-pot using a combination of heterogeneous metal and enzyme catalysts. Here reagents, catalysts, and different conditions can be introduced throughout the one-pot procedure involving multistep catalytic tandem operations. Several novel cocatalytic relay sequences (reductive amination/amidation, aerobic oxidation/reductive amination/amidation, reductive amination/kinetic resolution and reductive amination/dynamic kinetic resolution) were developed. They were next applied to the direct synthesis of various biologically and optically active amines or amides in one-pot from simple aldehydes, ketones, or alcohols, respectively.
- Palo-Nieto, Carlos,Afewerki, Samson,Anderson, Mattias,Tai, Cheuk-Wai,Berglund, Per,Córdova, Armando
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p. 3932 - 3940
(2016/07/06)
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- Whole-Cell Biocatalysts for Stereoselective C-H Amination Reactions
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Enantiomerically pure chiral amines are ubiquitous chemical building blocks in bioactive pharmaceutical products and their synthesis from simple starting materials is of great interest. One of the most attractive strategies is the stereoselective installation of a chiral amine through C-H amination, which is a challenging chemical transformation. Herein we report the application of a multienzyme cascade, generated in a single bacterial whole-cell system, which is able to catalyze stereoselective benzylic aminations with ee values of 97.5 %. The cascade uses four heterologously expressed recombinant enzymes with cofactors provided by the host cell and isopropyl amine added as the amine donor. The cascade presents the first example of the successful de novo design of a single whole-cell biocatalyst for formal stereoselective C-H amination.
- Both, Peter,Busch, Hanna,Kelly, Paul P.,Mutti, Francesco G.,Turner, Nicholas J.,Flitsch, Sabine L.
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p. 1511 - 1513
(2016/02/14)
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- The efficient solvent-free reduction of oximes to amines with NaBH3CN catalyzed by ZrCl4/nano Fe3O4 system
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Reduction of various aldoximes and ketoximes to the corresponding amines was carried out easily and efficiently with NaBH3CN in the presence of ZrCl4/nano Fe3O4 system. The reactions were carried out under solvent-free conditions at room temperature or 75-80°C to afford amines in high to excellent yields.
- Sadighnia, Leila,Zeynizadeh, Behzad
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p. 873 - 878
(2015/03/18)
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- A Single Lipase-Catalysed One-Pot Protocol Combining Aminolysis Resolution and Aza-Michael Addition: An Easy and Efficient Way to Synthesise β-Amino Acid Esters
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A novel one-pot protocol combining aza-Michael addition and aminolysis resolution was developed to obtain chiral β-amino acid esters with lipase B from Candida antarctica (CAL-B) as the only catalyst. This method is conducted under mild reaction conditions and is very easy to handle. After a series of detailed optimization studies, ten racemic aromatic or aliphatic amines were subjected to this one-pot procedure, and twelve chiral β-amino acid esters and ten chiral amides were successfully synthesised with excellent ee values in theoretical yields. Scaled-up procedures also worked without apparent reduction in reaction rate or enantioselectivity, which makes this method suitable for large-scale production of chiral β-amino acid esters. A one-pot protocol for simultaneous synthesis of chiral β-amino acid esters and amides was developed by combining single lipase B from Candida antarctica (CAL-B) catalysed aza-Michael addition and aminolysis resolution. This method requires mild reaction conditions and is very easy to handle. Chiral β-amino acid esters and chiral amides were obtained with excellent ee values and in theoretical yields.
- Xu, Fan,Wu, Qiongsi,Chen, Xiaoyang,Lin, Xianfu,Wu, Qi
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supporting information
p. 5393 - 5401
(2015/08/24)
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- Bioinspired organocatalytic aerobic C-H oxidation of amines with an ortho -quinone catalyst
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A simple bioinspired ortho-quinone catalyst for the aerobic oxidative dehydrogenation of amines to imines is reported. Without any metal cocatalysts, the identified optimal ortho-quinone catalyst enables the oxidations of α-branched primary amines and cyclic secondary amines. Mechanistic studies have disclosed the origins of different performances of ortho-quinone vs para-quinone in biomimetic amine oxidations.
- Qin, Yan,Zhang, Long,Lv, Jian,Luo, Sanzhong,Cheng, Jin-Pei
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p. 1469 - 1472
(2015/03/30)
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- Liquid chromatographic resolution of fendiline and its analogues on a chiral stationary phase based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid
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Fendiline, an effective anti-anginal drug for the treatment of coronary heart diseases, and its sixteen analogues were resolved on a CSP based on (+)-(18-crown-6)-2,3,11,12-tetracarboxylic acid. Fendiline was resolved quite well with the separation factor (α) of 1.25 and resolution (RS ) of 1.55 when a mobile phase consisting of methanol-acetonitrile-trifluoroacetic acid-triethylamine at a ratio of 80/20/0.1/0.5 (v/v/v/v) was used. The comparison of the chromatographic behaviors for the resolution of fendiline and its analogues indicated that the 3,3-diphenylpropyl group bonded to the secondary amino group of fendiline is important in the chiral recognition and the difference in the steric bulkiness between the phenyl group and the methyl group at the chiral center of fendiline is also important in the chiral recognition.
- Lee, Ga Ram,Hyun, Myung Ho
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p. 21386 - 21397
(2015/02/19)
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- Enantioselective synthesis of (R)-2-arylpropanenitriles catalysed by ene-reductases in aqueous media and in biphasic ionic liquid-water systems
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The enantioselective reduction of α-methylene nitrile derivatives catalysed by ene-reductases affords the corresponding (R)-2-arylpropanenitriles with high conversion values. The reaction is investigated either in aqueous medium (with an organic cosolvent or by loading the substrate onto hydrophobic resins) or in a biphasic ionic liquid-water system. The use of ionic liquids, herein with isolated ene-reductases, is found to improve the work-up and the substrate recovery method. The synthetic manipulation of the final chiral nitrile derivatives indicates how this biocatalysed method can be exploited for the preparation of a wide range of chiral compounds.
- Brenna, Elisabetta,Crotti, Michele,Gatti, Francesco G.,Manfredi, Alessia,Monti, Daniela,Parmeggiani, Fabio,Santangelo, Sara,Zampieri, Davila
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p. 2425 - 2431
(2014/08/18)
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- Modification of supported Pd catalysts by alkalic salts in the selective racemization and dynamic kinetic resolution of primary amines
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Supported Pd nanoparticles (PdNPs) were modified with various alkalic salts by incipient wetness impregnation method. The effect of the salts on the catalytic activity and selectivity behavior of Pd catalysts for the racemization of (S)-1-phenylethylamine was investigated. The presence of alkalic salts can greatly enhance the selectivity of Pd catalysts, without significantly decreasing the catalytic activity. This modification method is suitable for PdNPs supported on various supports, such as micro/mesoporous silica and activated carbon. Combined with the immobilized lipases (Novozyme 435), this catalyst system can efficiently catalyze the dynamic kinetic resolution (DKR) of 1-phenylethylamine with yield and enantioselectivity up to 97% and 99%, respectively. The Royal Society of Chemistry.
- Jin, Qianru,Jia, Guoqing,Zhang, Yanmei,Li, Can
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p. 464 - 471
(2014/02/14)
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- Enhancing thermostability and organic solvent tolerance of ω-transaminase through global incorporation of fluorotyrosine
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Here, we have utilized the incorporation of non-canonical amino acids as a tool kit to improve enzyme properties for organic synthesis applications. The global incorporation of 3-fluorotyrosine (FY) into ω-transaminase (ω-TA) to give ω-TA[FY] enhanced the thermostability and organic solvent tolerance without altering substrate specificity and enantioselectivity. Moreover, ω-TA[FY] was able to completely convert 25 mM of acetophenone into (S)-1-phenylethylamine (ee>99%) in the presence of 20% DMSO (v/v) which is 2-fold higher when compared to wild-type ω-TA.
- Deepankumar, Kanagavel,Shon, Minsu,Nadarajan, Saravanan Prabhu,Shin, Giyoung,Mathew, Sam,Ayyadurai, Niraikulam,Kim, Byung-Gee,Choi, Sei-Hyun,Lee, Sang-Hyeup,Yun, Hyungdon
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p. 993 - 998
(2014/04/03)
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- A highly fluorescent metallosalalen-based chiral cage for enantioselective recognition and sensing
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A highly fluorescent coordination cage [Zn8L4I 8] has been constructed by treating enantiopure pyridyl- functionalized metallosalalen units (L) with zinc(II) iodide and characterized by a variety of techniques including microanalysis, thermogravimetric analysis (TGA), circular dichroism (CD) spectroscopy, and single-crystal and powder X-ray diffraction. Strong intermolecular π-π, CH-π, and CH-I interactions direct packing of the cage molecules to generate a 3D polycage network interconnected by pentahedral cages formed by adjacent pentamers. The cage has an amphiphilic helical cavity decorated with chiral NH functionalities capable of interactions with guest species such as saccharides. The fluorescence of the cage was greatly enhanced by five enantiomeric saccharides in solution, with enantioselectivity factors of 2.480-4.943, and by five enantiomeric amines in the solid state, with enantioselective fluorescence enhancement ratios of 1.30-3.60. This remarkable chiral sensing of both saccharides and amines with impressive enantioselectivity may result from the steric confinement of the cavity as well as its conformational rigidity. It holds great promise for the development of novel chiral cage materials for sensing applications. Cage-based chiral sensor: A highly fluorescent coordination cage [Zn8L 4I8] can be prepared from enantiopure pyridyl- functionalized metallosalalen units (L). The cage has an amphiphilic helical cavity decorated with chiral NH functionalities and supramolecular interactions generate a 3D polycage network interconnected by pentahedral cages formed by adjacent pentamers (see graphic). The fluorescence of the cage is greatly enhanced either in solution or in the solid state in the presence of enantiomeric saccharides or amines, respectively, with significant enantioselectivity factors.
- Dong, Jinqiao,Zhou, Yanfang,Zhang, Fangwei,Cui, Yong
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supporting information
p. 6455 - 6461
(2014/06/09)
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- One-pot one-step deracemization of amines using ω-transaminases
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In this study, we developed a one-pot one-step deracemization method for the production of various enantiomerically pure amines using two opposite enantioselective ω-TAs. Using this method, various aromatic amines were successfully converted to their (R)-forms (>99%) with good conversion.
- Shin, Giyoung,Mathew, Sam,Shon, Minsu,Kim, Byung-Gee,Yun, Hyungdon
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p. 8629 - 8631
(2013/09/23)
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- Efficient racemization of 1-phenylethylamine and its derivatives
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We report on simple and efficient procedure for the racemization of 1-phenylethylamine and its derivatives. In the presence of trichloroisocyanuric acid, N-chloroimine derivative is formed as the intermediates, with subsequent hydrogenation catalyzed by Pd-C leading to the racemic product.
- Xiong, Xiaoxia,Xu, Xinliang,Zhou, Yifeng,Weng, Chenchen
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p. 2402 - 2405
(2014/03/21)
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- Asymmetric synthesis of nonracemic primary amines via spiroborate-catalyzed reduction of pure (E)- and (Z)-O-benzyloximes: Applications toward the synthesis of calcimimetic agents
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Highly enantiopure (1-aryl)- and (1-naphthyl)-1-ethylamines were synthesized by the borane-mediated reduction of single-isomeric (E)- and (Z)-O-benzyloxime ethers using the stable spiroborate ester derived from (S)-diphenyl valinol and ethylene glycol as the chiral catalyst. Primary (R)-arylethylamines were prepared by the reduction of pure (Z)-ethanone oxime ethers in up to 99% ee using 15% of catalyst. Two convenient and facile approaches to the synthesis of new and known calcimimetic analogues employing enantiopure (1-naphthalen-1-yl)ethylamine as chiral precursor are described.
- Ou, Wenhua,Espinosa, Sandraliz,Meléndez, Héctor J.,Farré, Silvia M.,Alvarez, Jaime L.,Torres, Valerie,Martínez, Ileanne,Santiago, Kiara M.,Ortiz-Marciales, Margarita
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p. 5314 - 5327
(2013/07/25)
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- Nickel nanoparticles as racemization catalysts for primary amines
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By combining bases that are known to racemize benzylic amines with a nickel(II) salt, active nickel nanoparticles were obtained that can be used as catalysts in the racemization of both aliphatic and benzylic primary amines. The nanoparticles are stable in the ionic liquid tetrabutylammonium bromide and can complete most racemizations within a few hours with excellent selectivity. The problem of the incompatibility of the strongly reducing racemization catalyst and the enzymatic amine resolution catalyst was overcome by using a two-pot system with a biphasic racemization step. Consecutive contact of a nonane layer that contained the amine with the acylating enzyme and with the racemizing Ni nanoparticles in the ionic liquid allowed the 50 % amide yield limit of a kinetic resolution to be successfully surpassed. Copyright
- Geukens, Inge,Plessers, Eva,Seo, Jin Won,De Vos, Dirk E.
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p. 2623 - 2628
(2013/07/11)
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- Cyclohexylamine oxidase as a useful biocatalyst for the kinetic resolution and dereacemization of amines
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The biocatalytic performance of a cloned cyclohexylamine oxidase derived from Brevibacterium oxydans IH-35A towards structurally different amines was investigated. Cycloalkyl primary amines, alkyl aryl amines, and α-carbon-substituted aliphatic amines were identified as suitable substrates for the biocatalyst based on an activity assay. Kinetic resolutions of several amines by either recombinant whole cells or crude enzyme extracts prepared therefrom gave enantiomerically pure (R)-amines besides the corresponding ketones. When cyclohexylamine oxidase in combination with a borane-ammonia complex as reducing agent was applied to the deracemization of several substrates, excellent enantiomeric ratios (>99:1) and good isolated yields (62%-75%) of the corresponding (R)-amines were obtained.
- Leisch, Hannes,Grosse, Stephan,Iwaki, Hiroaki,Hasegawa, Yoshie,Lau, Peter C.K.
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experimental part
p. 39 - 45
(2012/03/07)
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- Organocatalytic asymmetric biomimetic transamination of aromatic ketone to optically active amine
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An asymmetric biomimetic transamination of aromatic ketones to optically active amines with o-HOPhCH2NH2 as amine source catalyzed by hydroquinine-derived chiral base is described. Up to 85% ee was obtained.
- Xie, Ying,Pan, Hongjie,Xiao, Xiao,Li, Songlei,Shi, Yian
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supporting information
p. 8960 - 8962,3
(2012/12/12)
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- Organocatalytic asymmetric biomimetic transamination of aromatic ketone to optically active amine
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An asymmetric biomimetic transamination of aromatic ketones to optically active amines with o-HOPhCH2NH2 as amine source catalyzed by hydroquinine-derived chiral base is described. Up to 85% ee was obtained.
- Xie, Ying,Pan, Hongjie,Xiao, Xiao,Li, Songlei,Shi, Yian
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supporting information
p. 8960 - 8962
(2013/01/15)
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- A rapid and practical protocol for solvent-free reduction of oximes to amines with NaBH4/ZrCl4/Al2O3 system
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Solvent-free reduction of various aldoximes and ketoximes to the corresponding amines was performed easily and efficiently with NaBH4 in the presence of ZrCl4 supported on Al2O3. The reactions were carried out rapidly (within 2 min) at room temperature to afford the amines in high to excellent yields.
- Zeynizadeh, Behzad,Kouhkan, Mehri
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experimental part
p. 3448 - 3452
(2012/02/01)
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- A new and convenient method for reduction of oximes to amines with NaBH3CN in the presence of MoCl5/NaHSO4? H2O system
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Various aldoximes and ketoximes were efficiently reduced to their corresponding amines with NaBH3CN in the presence of MoCl 5/NaHSO4?H2O system. Reduction reactions were carried out in refluxing EtOH or DMF within 0.3-3.8 h to afford the amines in high to excellent yields.
- Kouhkan, Mehri,Zeynizadeh, Behzad
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experimental part
p. 3323 - 3326
(2012/02/04)
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- COMPOSITIONS AND METHODS FOR CYCLOFRUCTANS AS SEPARATION AGENTS
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The present invention relates to derivatized cyclofructan compounds, compositions comprising derivatized cyclofructan compounds, and methods of using compositions comprising derivatized cyclofructan compounds for chromatographic separations of chemical species, including enantiomers. Said compositions may comprise a solid support and/or polymers comprising derivatized cyclofructan compounds.
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Page/Page column 45-49; 62
(2010/12/31)
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- Heterogeneous raney nickel and cobalt catalysts for racemization and dynamic kinetic resolution of amines
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Raney metals were studied as heterogeneous catalysts for racemization and dynamic kinetic resolution (DKR) of chiral amines, as an alternative to metals like palladium or ruthenium. Both Raney nickel and cobalt were able to selectively racemize various chiral amines with high selectivity. In the racemization of benzylic primary amines, the minor formation of side products, e.g., secondary amines, can be suppressed by varying the hydrogen pressure. In the racemization of aliphatic amines over Raney catalysts, the selectivity is very high, with the enantiomeric amine as the sole product. DKR of racemic aliphatic amines can be performed with immobilized Candida antarctica lipase B and Raney nickel in one pot; for 2-hexylamine, a yield of 95% of the acetylated amide was achieved, with 97% ee. Attention is devoted to the compatibility of the enzyme and the metal catalyst during the DKR. For benzylic primary amines, a two-pot process is proposed in which the liquid is alternatingly shuttled between two vessels containing the solid racemization catalyst and the biocatalyst. After 4 such cycles, the amide of (R)-1-phenylethylamine was obtained with 94% yield and more than 90% ee.
- Parvulescu, Andrei N.,Jacobs, Pierre A.,De Vos, Dirk E.
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scheme or table
p. 113 - 121
(2009/04/16)
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- Palladium catalysts on alkaline-earth supports for racemization and dynamic kinetic resolution of benzylic amines
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Palladium catalysts on alka-line-earth supports were studied as new heterogeneous catalysts for racemization of chiral benzylic amines such as 1-phenylethylamine. Particularly 5% Pd/BaSO4 and 5% Pd/CaCO 3 were able to selectively racemize amines, with minimal formation of secondary amines or hydrogenolysis to ethylbenzene. In contrast, these side reactions were pronounced on Pd/C. A reaction mechanism is proposed that is consistent with the reaction kinetics. The catalyst activity was found to depend on the number of available surface Pd atoms, determined by titration with CO. The selectivity crucially depends on the rate of condensation of the amine and the primary imine. which is highest on Pd/C. The racemization catalysts were combined in one pot with an immobilized lipase to perform dynamic kinetic resolution of chiral amines. High yields (up to 88%) of essentially enantiopure amides were obtained in a single step. The chemo-enzymatic catalyst system proved to be stable and could be reused without losing the initial activity.
- Parvulescu, Andrei N.,Jacobs, Pierre A.,De Vos, Dirk E.
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p. 2034 - 2043
(2008/02/03)
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- Synthesis and chiral recognition ability of O-phenyl ethylphosphonothioic acid with a conformationally flexible phenoxy group for CH/π interaction
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Enantiopure O-phenyl ethylphosphonothioic acid 1 was easily obtained by the enantioseparation of racemic 1, which was prepared from commercially available phosphorothioic trichloride in four steps. Enantiopure 1 was found to show an excellent chiral recognition ability for various 1-arylethylamine derivatives during the diastereomeric salt formation. In particular, enantiopure 1 was able to recognize the chirality of o- and m-substituted 1-arylethylamine derivatives, of which the chirality is generally difficult to establish by conventional resolving agents. X-ray crystallographic analyses of the less-soluble diastereomeric salts revealed that the conformation of the phenoxy group in enantiopure 1 could change in the diastereomeric salt crystals and that the excellent chiral recognition ability of enantiopure 1 resulted from the effective CH/π interaction of the phenoxy phenyl group.
- Kobayashi, Yuka,Maeda, Jin,Morisawa, Fumi,Saigo, Kazuhiko
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p. 967 - 974
(2007/10/03)
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