17199-29-0Relevant articles and documents
Normal Pressure Double Carbonylation of Aryl Halides Using Cobalt(II) Chloride in the Presence of either Sodium Sulfide or Sodium Borohydride
Itoh, Kenji,Miura, Masahiro,Nomura, Masakatsu
, p. 4151 - 4152 (1988)
Tetracarbonylcobaltate ion generated by a treatment of cobalt(II) chloride with either sodium sulfide or sodium borohydride under a normal pressure of carbon monoxide was capable of catalyzing carbonylation of aryl halides in the presence of calcium hydroxide and methyl iodide to give arylglyoxylic acids in good selectivity.
A combination of phase transfer catalyst and ultrasonic irradiation promotes synthesis of mandelic acid
Zhang, Yu-Quan,Zheng, Xu-Dong,Gai, Ke,Li, Yan-Chun,Cheng, Dong-Ping
, p. 455 - 457 (2014)
A combination of phase transfer catalyst and ultrasonic irradiation used to promotes synthesis of mandelic acid from benzaldehyde with chloroform. The main advantages of this method are that the reaction time is much shorter and the yield is higher than t
Improved solution- and solid-phase preparation of hydroxamic acids from esters
Ho, Chih Y.,Strobel, Eric,Ralbovsky, Janet,Galemmo Jr., Robert A.
, p. 4873 - 4875 (2005)
The addition of small amounts of solid KCN to solution and solid-phase esters in THF/MeOH/50% aqueous NH2OH increases the efficiency of their transformation to the corresponding hydroxamic acids.
Solvent-induced reversed stereoselectivity in reciprocal resolutions of mandelic acid and erythro -2-amino-1,2-diphenylethanol
Shitara, Hiroaki,Shintani, Toshiki,Kodama, Koichi,Hirose, Takuji
, p. 9309 - 9316 (2013)
Solvent-induced chirality switching in reciprocal optical resolution between mandelic acid (1) and erythro-2-amino-1,2-diphenylethanol (2) has been demonstrated. The stereochemistry of the deposited salts was controlled by changing the crystallization solvent from 1-PrOH or 1-BuOH to 1,4-dioxane. It was revealed from 1H NMR spectra, thermogravimetric analysis, and X-ray crystallography of the salts that an equimolar amount of the crystallization solvent was incorporated in each diastereomeric salt. On the basis of the crystal structures, it was found that both the hydrogen-bonding ability and the size of the solvent molecule played an important role. Differences in the formed hydrogen-bonding networks (columnar or sheetlike structure) and their packing manner were found to be crucial for the reversed stereoselectivity. Furthermore, pseudopolymorphic salt crystals that incorporated 1,4-dioxane were obtained during the enantioseparation of racemic 2, and their solid-state properties were examined by measurement of their IR spectra. This solvent-induced dual stereocontrol technique was successfully applied to the successive resolution process, eliminating the need to change the resolving agent for access to both enantiomers of 1 and 2.
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Doering,Taylor,Schoenewaldt
, p. 455 (1948)
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Light-assisted preparation of a cyclodextrin-based chiral stationary phase and its separation performance in liquid chromatography
Tang, Qi,Yu, Bing,Gao, Lilong,Cong, Hailin,Zhang, Shuai
, p. 1115 - 1120 (2018)
A cyclodextrin-based chiral stationary phase (CD-CSP) is one of the most widely applied CSPs due to its powerful enantioseparation ability. In this study, a facile method was developed to prepare a CD-CSP via carboxyl methyl β-cyclodextrin (CD-COOH) and diazo-resin (DR). Monodisperse silica particles were synthesized using a modified St?ber method. Then DR and CD-COOH were coated on the silica particles via ionic bonding successively and UV light was finally used to couple silica, DR and CD-COOH and the ionic bonds turned into covalent bonds. The resultant CD-DR silica particles were characterized using Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA) and scanning electron microscopy (SEM). The enantioselectivity of the CD@SiO2 particles was explored in reversed phase high-performance liquid chromatography (RP-HPLC). Baseline separation of chiral drugs was achieved and the effects of separation parameters (elution mode, buffer and analyte mass) were investigated in detail. By using water soluble non-toxic DR to replace a highly toxic and moisture sensitive silane agent to modify silica microspheres, this light-assisted strategy can provide a green and effective technique to manufacture packing materials for enantioseparation applications.
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Walker,Krieble
, p. 1437 (1909)
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Designing of amino functionalized imprinted polymeric resin for enantio-separation of (±)-mandelic acid racemate
Alhawiti, Aliyah S.,Monier,Elsayed, Nadia H.
, (2021)
S-Mandelic acid (MA) enantio-selective resinous material functionalized with –NH2 groups has been developed and effectively utilized in chiral separation of (±)-MA racemate solution. S-MA has first combined with the polymerizable p-aminophenol and form the corresponding amide derivative, which was then polymerized with phenol/formalin using HCl as a catalyst. The stereo-selective –NH2 functionalized binding sites were then generated within the resin upon the alkaline degradation of the amide linkages followed by acidic treatments that will expel the resin incorporated S-MA out of the polymeric material to get the S-MA imprinted polymer (S-MAPR). The synthesized S-MA chiral amide derivative along with the developed polymeric resin was investigated by various techniques including FTIR and NMR spectra that confirmed the executed chemical modifications. In addition, the morphological appearance of the obtained resins were observed using SEM images. Moreover, the S-MAPR resin was examined to optimize the enantio-selective separation conditions and the studies indicated that the adsorption reached the highest value at pH 7 and the maximum capacity was 243 ± 1 mg/g. In addition, the chiral separation of (±)-MA racemic solution was successfully executed by the S-MAPR separation column with 55% and 82% enantiomeric excess of R- and S-MA within both the initial loading and recovery eluant solutions, respectively.
Whole Cell-Based Cascade Biotransformation for the Production of (S)-Mandelic Acid from Styrene, L-Phenylalanine, Glucose, or Glycerol
Lukito, Benedict Ryan,Sekar, Balaji Sundara,Wu, Shuke,Li, Zhi
, p. 3560 - 3568 (2019)
(S)-Mandelic acid is a useful and high value chemical with many synthetic applications, but its synthesis often requires the use of toxic cyanide. Here, we report the development of several cyanide-free methods to prepare (S)-mandelic acid via cascade biotransformation. Enhanced production of (S)-mandelic acid from styrene via 4-step enzyme cascades was achieved with Escherichia coli (A-M1_R-M2) cells, giving 118–144 mM (18–21.9 g/L, 72–79% yield) product. The process was scaled up to 1.5 L to produce 140 mM (21.3 g/L) of (S)-mandelic acid in 70% yield. A strategy with the recycling and reuse of Escherichia coli cells, unreacted substrate, and organic solvent was developed to enhance the productivity of (S)-mandelic acid through repeated batches, affording 190 mM (95% yield) and 328 mM (82% yield) product in two and four batches, respectively. (S)-mandelic acid was also produced from bio-derived L-phenylalanine via 6-step enzyme cascades. Biotransformation of L-phenylalanine with Escherichia coli (LZ37) cells expressing all enzymes for the reactions gave 160 mM (S)-mandelic acid in 80% yield. Moreover, (S)-mandelic acid were synthesized from glycerol or glucose via L-phenylalanine biosynthesis pathway and the 6-step enzyme cascade. Coupling of Escherichia coli (NST74-Phe) with Escherichia coli (LZ37) enabled the sustainable production of 63 mM (10 g/L) or 52 mM (8 g/L) (S)-mandelic acid from renewable feedstocks glycerol and glucose, respectively. (Figure presented.).
Asymmetric ammonolysis of (R/S)-mandelic acid by immobilized lipases via direct amidation of mandelic acid in biphasic media
Yildirim, Deniz,Tükel, S. Seyhan
, p. 251 - 258 (2014)
We have investigated the direct enantioselective amidation of mandelic acid with ammonia, catalyzed by a variety of commercial lipases including those from Candida rugosa, Mucor miehei, Pseudomonas sp., Rhizomucor miehei, and Thermomyces lanuginosus coval
Construction of Recombinant Escherichia coli catalysts which simultaneously express an (S)-oxynitrilase and different nitrilase variants for the synthesis of (S)-mandelic acid and (S)-mandelic amide from benzaldehyde and cyanide
Sosedov, Olga,Matzer, Kathrin,Buerger, Sibylle,Kiziak, Christoph,Baum, Stefanie,Altenbuchner, Josef,Chmura, Andrzej,Van Rantwijk, Fed,Stolz, Andreas
, p. 1531 - 1538 (2009)
Recombinant Escherichia coli strains were constructed which simultaneously expressed the genes encoding the (S)-oxynitrilase from cassava (Manihot esculenta) together with the wild-type or a mutant variant of the arylacetonitrilase from Pseudomonas fluorescens EBC191 in a single organism under the control of a rhamnose-inducible promoter. The whole cell catalysts obtained converted benzaldehyde and potassium cyanide in aqueous media at pH 5.2 mainly to (S)-mandelic acid and/or (S)-mandelic amide and synthesized only low amounts of the corresponding (R)-enantiomers. The conversion of benzaldehyde and potassium cyanide (KCN) by a whole-cell catalyst simultaneously expressing the (5)-oxynitrilase and the wild-type nitrilase resulted in a ratio of (S)-mandelic acid to (S)-mandelic amide of about 4:3. This could be explained by the strong nitrile hydratase activity of the wild-type nitrilase with (S)-mandelonitrile as substrate. The relative proportion of (S)-mandelic amide formed in this system was significantly increased by coexpressing the (S)-oxynitrilase with a carboxy-terminally truncated variant of the nitrilase. This whole-cell catalyst converted benzaldehyde and KCN to mandelic amide and mandelic acid in a ratio of about 9:1. The ee of the (S)-mandelic amide formed was calculated to be 95%.
Symmetrical cleavage of a racemicester by a liver esterase of the Cebus
BAMANN,GEBLER
, p. 82 - 85 (1960)
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Novel catalytic tandem isomerisation/cyclisation reaction of α-methallyloxy carboxylic acids
Chaminade, Xavier,Coulombel, Lydie,Olivero, Sandra,Dunach, Elisabet
, p. 3554 - 3557 (2006)
A new tandem isomerisation/cyclisation of α-methallyloxy carboxylic acids leading to substituted 1,3-dioxolan-4-ones in 60-70 % yields was catalysed by Cu(OTf)2 or Al(OTf)3. Extension to the synthesis of oxathiolanones and oxathianon
Enantioseparation of mandelic acid and α-Cyclohexylmandelic acid using an alcohol/salt-based aqueous two-Phase system
Li, Fen-Fang,Tan, Zhi-Jian,Guo, Zhi-Feng
, p. 1539 - 1545 (2014)
An alcohol/salt-based aqueous two-phase system (ATPS) was employed for enantioseparation of (R,S)-mandelic acid (MA) and (R,S)-a-cyclohexylmandelic acid (a-CHMA). Sulfonated β-cyclodextrin (Sf-β-CD) with different degrees of substitution (DS) was consider
Direct enantioseparation of mandelic acid by high-performance liquid chromatography using a phenyl column precoated with a small amount of cyclodextrin additive in a mobile phase
Watanabe, Yuri,Mikami, Ikko,Yamamoto, Atsushi,Aizawa, Sen-ichi,Taga, Atsushi,Mochizuki, Naoki,Ishihara, Yoshimi,Kodama, Shuji
, p. 1020 - 1029 (2020)
Direct enantioseparation of mandelic acid by high-performance liquid chromatography (HPLC) with a reversed phase column and a mobile phase containing a small amount of hydroxylpropyl-β-cyclodextrin (HP-β-CD) was studied as an efficient method for saving consumption of the CD additive. As a result, it was proposed that racemic mandelic acid can be analyzed with a phenyl column by using a mobile phase composed of 10 mM ammonium acetate buffer (pH 4.2) and 0.02% (w/v) HP-β-CD at a flow rate of 1.0 mL/min at 40°C after the passage of 10 mM ammonium acetate buffer (pH 4.2) containing 0.1% (w/v) HP-β-CD as a precoating mobile phase for 60 min. It is suggested that HP-β-CD is bound with a phenyl group on the surface of the stationary phase to allow a phenyl column to act as a transient chiral column, and injected mandelic acid can form the ternary complex with the adsorbed HP-β-CD. The longer retention time of D-mandelic acid than the L-isomer for HPLC can be explained from the higher stability of the HP-β-CD complex with D-mandelic acid, which was confirmed by CE experiment with HP-β-CD as a selector. The efficiency of a phenyl column compared with other stationary phases was also discussed.
Electrocatalytic reduction of benzoylformic acid mediated by methyl viologen
Park, Joon Woo
, p. 2637 - 2638 (1995)
Benzoylformic acid is reduced electrocatalytically to mandelic acid in excellent yield in the presence of methyl viologen of which two-electron reduction product behaves as active reductant, and the presence of β-CD or its derivative induces enantioselect
Chirality switching in optical resolution of mandelic acid in C1-C4 alcohols: Elucidation of solvent effects based on x-ray crystal structures of diastereomeric salts
Kodama, Koichi,Shitara, Hiroaki,Hirose, Takuji
, p. 3549 - 3556 (2014)
Chirality switching in the optical resolution of mandelic acid (MA) using (1R,2S)-2-amino-1,2-diphenylethanol (ADPE) in C1-C4 alcohols is demonstrated herein. Recrystallization of the diastereomeric mixture of the MA salts from longer alcohol solvents (n-PrOH, s-BuOH, i-BuOH, and n-BuOH) produced the (R)-MA salt, whereas the (S)-MA salt was preferentially deposited from shorter alcohol solvents (MeOH, EtOH, i-PrOH, and t-BuOH). Thermogravimetric analysis and 1H NMR spectroscopy showed that all the solvents employed were incorporated in the diastereomeric salts and the stability of the incorporated alcohols increased with an increase in the effective surface area of their alkyl chains. The X-ray crystal structures of the eight solvated diastereomeric salt pairs revealed that the type of hydrogen-bonding network (sheetlike or columnar) and the arrangement of the columnar structures were controlled by the length of the included alcohol. By comparison of the two diastereomeric MA salt crystal structures, their relative stability to display chirality switching was investigated.
HYDRATION OF CYANOHYDRINS IN WEEKLY ALKALINE SOLUTIONS OF BORIC ACID SALTS
Jammot, Jacqueline,Pascal, Robert,Commeyras, Auguste
, p. 563 - 564 (1989)
α-Hydroxyamides and α-hydroxyacids were prepared in satisfactory yield by heating aldehyde-derived cyanohydrins in aqueous solution in the presence of borax or alkaline borates.
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Walker
, p. 472 (1903)
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(R)-mandelic acid (S)-alanine hemihydrate
Hu, Zi-Qiang,Xu, Duan-Jun,Xu, Yuan-Zhi,Wu, Jing-Yun,Chiang, Michael Y.
, p. o612-o614 (2002)
Crystals of the title complex, C3H7NO2·C8H8O 3·0.5H2O, were obtained from an aqueous solution containing racemic mandelic acid and (S)-alanine. The unit cell includes two independent molecular complexes and one water molecule. The structure formed by (R)-mandelic acid and (S)-alanine in a 1:1 molar ratio shows the successful optical separation of racemic mandelic acid. Strong hydrogen bonding, with a rather short O...O separation of 2.494 (3) A, is observed between the carboxyl and carboxylate groups. A structural comparison suggests that the strong hydrogen bonding affects the neighbouring covalent bond.
Application of a recombinant Escherichia coli whole-cell catalyst expressing hydroxynitrile lyase and nitrilase activities in ionic liquids for the production of (S)-mandelic acid and (S)-mandeloamide
Baum, Stefanie,Van Rantwijk, Fred,Stolz, Andreas
, p. 113 - 122 (2012)
The conversion of benzaldehyde and cyanide into mandelic acid and mandeloamide by a recombinant Escherichia coli strain which simultaneously expressed an (S)-hydroxynitrile lyase (oxynitrilase) from cassava (Manihot esculenta) and an aryl-acetonitrilase from Pseudomonas fluorescens EBC191 was studied. Benzaldehyde exhibited a pronounced inhibitory effect on the nitrilase activity in concentrations ≥25 mM. Therefore, it was tested if two-phase systems consisting of a buffered aqueous phase and the ionic liquid 1-butyl-1-pyrrolidinium bis(trifluoromethanesulfonyl)imide (BMpl NTf 2) or 1-butyl-3-methylimidazolium hexafluorophosphate (BMim PF 6) could be used for the intended biotransformation. The distribution coefficients of the substrates, intermediates and products of the reaction were determined and it was found that BMpl NTf2 and BMim PF6 were highly efficient as substrate reservoirs for benzaldehyde. The recombinant E. coli strain was active in the presence of BMpl NTf2 or BMim PF6 phases and converted benzaldehyde and cyanide into mandelic acid and mandeloamide. The two-phase systems allowed the conversion of benzaldehyde dissolved in the ionic liquids to a concentration of 700 mM with product yields (=sum of mandelic acid and mandeloamide) of 87-100%. The cells were slightly more effective in the presence of BMpl NTf2 than in the presence of BMim PF6. In both two-phase systems benzaldehyde and cyanide were converted into (S)-mandeloamide and (S)-mandelic acid with enantiomeric excesses ≥94%. The recombinant E. coli cells formed, in the two-phase systems with ionic liquids and increased substrate concentrations, higher relative amounts of mandelo-amide than in a purely aqueous system with lower substrate concentrations.
Alexander
, p. 289,293 (1947)
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Vogler
, p. 2111,2115 (1950)
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Bulcraig,Dawson
, p. 80,82, 84 (1943)
Discovery of a diverse set of esterases from hot spring microbial mat and sea sediment metagenomes
Ranjan, Ravi,Yadav, Manish Kumar,Suneja, Garima,Sharma, Rakesh
, p. 572 - 581 (2018)
Esterases are an important group of biocatalysts for synthetic organic chemistry. Functional metagenomics allows discovery of novel biocatalysts by providing access to the gene pool of the microbial community of a habitat. Two metagenomic libraries representing the gene pool of sea sediment and hot spring microbial mat were constructed. Functional screening of these libraries resulted in the isolation of total 8 clones with tributyrin hydrolytic activity. Sequence analysis revealed 10 putative lipolytic proteins with 42–99% homology to the protein sequences in the databases, nine of which represented six known esterase families. Four of the encoded proteins represented Family V and amongst others, one each represented the Family VIII, pectin acetylesterase, enterobactin esterase, G-D-S-L family and OsmC domain containing esterase. One unusual lipolytic protein possessed poly-(3-hydroxybutyrate) depolymerase domain fused to lipase/esterase domain. Two phylogenetically related esterases (MLC3 and SLC5) belonging to family V were expressed and purified to homogeneity. The enzymes exhibited environment-adapted temperature optimum and thermostability. MLC3 was able to stereoselectively hydrolyze R-methyl mandelate to produce R-mandelic acid, an important chiral building block, which suggests MLC3 has potential commercial application.
A Four-Step Enzymatic Cascade for Efficient Production of L-Phenylglycine from Biobased L-Phenylalanine
Yuan, Jifeng,Zhu, Yuling
, (2022/03/01)
Enantiopure amino acids are of particular interest in the agrochemical and pharmaceutical industries. Here, we report a multi-enzyme cascade for efficient production of L-phenylglycine (L-Phg) from biobased L-phenylalanine (L-Phe). We first attempted to engineer Escherichia coli for expressing L-amino acid deaminase (LAAD) from Proteus mirabilis, hydroxymandelate synthase (HmaS) from Amycolatopsis orientalis, (S)-mandelate dehydrogenase (SMDH) from Pseudomonas putida, the endogenous aminotransferase (AT) encoded by ilvE and L-glutamate dehydrogenase (GluDH) from E. coli. However, 10 mM L-Phe only afforded the synthesis of 7.21±0.15 mM L-Phg. The accumulation of benzoylformic acid suggested that the transamination step might be rate-limiting. We next used leucine dehydrogenase (LeuDH) from Bacillus cereus to bypass the use of L-glutamate as amine donor, and 40 mM L-Phe gave 39.97±3.84 mM (6.04±0.58 g/L) L-Phg, reaching 99.9 % conversion. In summary, this work demonstrates a concise four-step enzymatic cascade for L-Phg synthesis from biobased L-Phe, with a potential for future industrial applications.
Method for synthesizing mandelic acid
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Paragraph 0032; 0034-0035; 0037-0038; 0040-0041; 0043, (2021/02/06)
The invention relates to the technical field of compound preparation, and provides a method for synthesizing mandelic acid, which comprises the following steps: by using styrene as a basic raw material, trichloroisocyanuric acid as a chlorinating agent an
