90319-52-1

Basic information

• Product Name: (R)-(-)-4-Phenyl-2-oxazolidinone
• Synonyms: 2-OXAZOLIDINONE, 4-PHENYL-, (4R)-;(4R)-4-PHENYLOXAZOLIDIN-2-ONE;(4R)-4-PHENYL-1,3-OXAZOLIDIN-2-ONE;(4R)-PHENYL-2-OXAZOLIDINONE;(R)-(-)-4-PHENYL-2-OXAZOLIDINONE;(R)-(+)-4-PHENYL-2-OXAZOLIDINONE;(R)-4-PHENYL-2-OXAZOLIDINONE;S/R-4-BENZYL-2-OXAZOLIDINONE
• CAS NO: 90319-52-1
• Molecular Formula: C₉H₉NO₂
• Molecular Weight: 163.17
• EINECS: 1312995-182-4
• Product Categories: Oxazolidinone;Isoxazoles, Oxadiazoles, Oxazoles;chiral;Chiral Reagent;Aromatics Compounds;Asymmetric Synthesis;Chiral Building Blocks;Glycidyl Compounds, etc. (Chiral);Synthetic Organic Chemistry;Chiral chemicals;Peptide;Aromatics;Heterocycles;Asymmetric Synthesis;Chiral Auxiliaries;Oxazolidinone Derivatives
• Mol File: 90319-52-1.mol

Chemical Properties

• Melting Point: 131-133 °C(lit.)
• Boiling Point: 290.25°C (rough estimate)
• Flash Point: 199.953 °C
• Appearance: white to light yellow crystal powder
• Density: 1.2021 (rough estimate)
• Vapor Pressure: 7.79E-07mmHg at 25°C
• Refractive Index: -72 ° (C=1, AcOEt)
• Storage Temp.: Store at 0-5°C
• Solubility: Chloroform (Slightly), Ethyl Acetate, Methanol (Slightly)
• PKA: 12.05±0.40(Predicted)
• BRN: 4308995
• CAS DataBase Reference: (R)-(-)-4-Phenyl-2-oxazolidinone(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-(-)-4-Phenyl-2-oxazolidinone(90319-52-1)
• EPA Substance Registry System: (R)-(-)-4-Phenyl-2-oxazolidinone(90319-52-1)

Safety Data

• Hazard Codes: F+,Xi
• Statements: 12-36
• Safety Statements: 22-24/25-33-26-16-7/9
• WGK Germany: 3
• F: 3-10
• Hazardous Substances Data: 90319-52-1(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
(R)-(-)-4-Phenyl-2-oxazolidinone is used as a synthon for the synthesis of α-amino acids and β-lactam antibiotics. Its chiral nature and unique structural features make it an ideal candidate for the development of enantioselective synthetic routes to these important classes of compounds.
Used in Organic Synthesis:
(R)-(-)-4-Phenyl-2-oxazolidinone is used as a versatile building block in organic synthesis. Its ability to form stable intermediates and participate in various chemical reactions allows chemists to use it in the construction of complex organic molecules, including pharmaceuticals, agrochemicals, and other specialty chemicals.
Used in α-amino acid synthesis:
(R)-(-)-4-Phenyl-2-oxazolidinone is employed as a key intermediate in the synthesis of α-amino acids, which are essential building blocks for the formation of proteins and peptides. Its use in this application allows for the development of novel synthetic routes to enantiomerically pure α-amino acids, which are crucial for the production of biologically active peptides and proteins.
Used in β-lactam antibiotic preparation:
(R)-(-)-4-Phenyl-2-oxazolidinone is also used in the preparation of β-lactam antibiotics, a widely used class of antibiotics that includes penicillins, cephalosporins, and carbapenems. Its incorporation into the synthesis of these antibiotics can lead to the development of new, more effective, and potentially more selective β-lactam-based drugs.

InChI:InChI=1/C9H9NO2/c11-9-10-8(6-12-9)7-4-2-1-3-5-7/h1-5,8H,6H2,(H,10,11)/t8-/m0/s1

Upstream product

• 86217-38-1 4-phenyl-2-oxazolidinone 
• 124-38-9 carbon dioxide 
• 56613-80-0 D-2-phenylglycinol 
• 126610-77-3 (R)-tert-butyl N-<1-phenyl-2-<(p-toluenesulfonyl)oxy>ethyl>carbamate 
• 616-38-6 carbonic acid dimethyl ester 
• 105-58-8 Diethyl carbonate 
• 503-38-8 trichloromethyl chloroformate 
• 161533-41-1 ethyl (1R)-2-hydroxy-1-phenylethylcarbamate 
• 20989-17-7 Phenylglycinol 
• 57-13-6 urea 
• 67553-20-2 (+/-)-benzyl 2-hydroxy-1-phenylethylcarbamate 
• 850240-22-1 (R)-3-{(2R,3S)-2-Azido-3-(4-tert-butyl-phenyl)-3-[3-(2-methoxy-ethoxymethoxy)-phenyl]-propionyl}-4-phenyl-oxazolidin-2-one 
• 17126-67-9 (+)-(R)-tropic acid 
• 24424-99-5 di-tert-butyl dicarbonate 

Downstream Products

• 201300-96-1 (4'R)-2-bromo-1-(2'-oxo-4'-phenyloxazolidin-3'-yl)propan-1-one 
• 148766-15-8 (R,E)-3-but-2-enoyl-4-phenyloxazolidin-2-one 
• 92344-79-1 3-<(6-Methyl-3-cyclohexenyl)carbonyl>-4-phenyl-2-oxazolidinone 
• 92284-50-9 3-<(6-Methyl-3-cyclohexenyl)carbonyl>-4-phenyl-2-oxazolidinone 
• 151800-32-7 (3(3R),4R)-3-<3-(4'-Methoxyphenyl)butanoyl>-4-phenyl-2-oxazolidinone 
• 118166-27-1 (R)-3-((S)-6,7-Dichloro-2,3-dihydro-benzofuran-2-carbonyl)-4-phenyl-oxazolidin-2-one 
• 118196-05-7 (R)-3-((R)-6,7-Dichloro-2,3-dihydro-benzofuran-2-carbonyl)-4-phenyl-oxazolidin-2-one 
• 156721-18-5 (3(2E), 4R)-3-<3-(N-(2-mesitylenesulfonyl)-3-indolyl)-1-oxopropenyl>-4-phenyl-2-oxazolidinone 
• 90247-26-0 (R)-3-[(R)-8-Chloro-3-(2-fluoro-phenyl)-5,6-dihydro-furo[2',3':4,5]benzo[1,2-d]isoxazole-6-carbonyl]-4-phenyl-oxazolidin-2-one 
• 90247-27-1 (R)-3-[(S)-8-Chloro-3-(2-fluoro-phenyl)-5,6-dihydro-furo[2',3':4,5]benzo[1,2-d]isoxazole-6-carbonyl]-4-phenyl-oxazolidin-2-one 
• 155674-27-4 (R)-3-((R)-2-Chloromethyl-3,3-dimethyl-butyryl)-4-phenyl-oxazolidin-2-one 
• 112459-65-1 (4R)-cyclohexyl-2-oxazolidinone 
• 99333-53-6 ((R)-2-Oxo-4-phenyl-oxazolidin-3-yl)-acetic acid ethyl ester 
• 160538-64-7 (4S)-N-[(3S)-phenylbutanoyl]-4-phenyl-1,3-oxazolidin-2-one 

Relevant articles and documents

Catalytic enantioselective synthesis of β-amino alcohols by nitrene insertion

Chiral β-amino alcohols are important building blocks for the synthesis of drugs, natural products, chiral auxiliaries, chiral ligands and chiral organocatalysts. The catalytic asymmetric β-amination of alcohols offers a direct strategy to access this class of molecules. Herein, we report a general intramolecular C(sp3)-H nitrene insertion method for the synthesis of chiral oxazolidin-2-ones as precursors of chiral β-amino alcohols. Specifically, the ring-closing C(sp3)-H amination of N-benzoyloxycarbamates with 2 mol% of a chiral ruthenium catalyst provides cyclic carbamates in up to 99% yield and with up to 99% ee. The method is applicable to benzylic, allylic, and propargylic C-H bonds and can even be applied to completely non-activated C (sp3)-H bonds, although with somewhat reduced yields and stereoselectivities. The obtained cyclic carbamates can subsequently be hydrolyzed to obtain chiral β-amino alcohols. The method is very practical as the catalyst can be easily synthesized on a gram scale and can be recycled after the reaction for further use. The synthetic value of the new method is demonstrated with the asymmetric synthesis of a chiral oxazolidin-2-one as intermediate for the synthesis of the natural product aurantioclavine and chiral β-amino alcohols that are intermediates for the synthesis of chiral amino acids, indane-derived chiral Box-ligands, and the natural products dihydrohamacanthin A and dragmacidin A.[Figure not available: see fulltext.].

Chiral separation materials based on derivatives of 6-amino-6-deoxyamylose

In order to develop new type of chiral separation materials, in this study, 6-amino-6-deoxyamylose was used as chiral starting material with which 10 derivatives were synthesized. The amino group in 6-amino-6-deoxyamylose was selectively acylated and then the hydroxyl groups were carbamoylated yielding amylose 6-amido-6-deoxy-2,3-bis(phenylcarbamate)s, which were employed as chiral selectors (CSs) for chiral stationary phases of high-performance liquid chromatography. The resulted 6-amido-6-deoxyamyloses and amylose 6-amido-6-deoxy-2,3-bis(phenylcarbamate)s were characterized by IR, 1H NMR, and elemental analysis. Enantioseparation evaluations indicated that most of the CSs demonstrated a moderate chiral recognition capability. The 6-nonphenyl (6-nonPh) CS of amylose 6-cyclohexylformamido-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) showed the highest enantioselectivity towards the tested chiral analytes; the phenyl-heterogeneous (Ph-hetero) CS of amylose 6-(4-methylbenzamido)-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) baseline separated the most chiral analytes; the phenyl-homogeneous (Ph-homo) CS of amylose 6-(3,5-dimethylbenzamido)-6-deoxy-2,3-bis(3,5-dimethylphenylcarbamate) also exhibited a good enantioseparation capability among the developed CSs. Regarding Ph-hetero CSs, the enantioselectivity depended on the combination of the substituent at 6-position and that at 2- and 3-positions; as for Ph-homo CSs, the enantioselectivity was related to the substituent at 2-, 3-, and 6-positions; with respect to 6-nonPh CSs, the retention factor of most analytes on the corresponding CSPs was lower than that on Ph-hetero and Ph-homo CSPs in the same mobile phases, indicating π–π interactions did occur during enantioseparation. Although the substituent at 6-position could not provide π–π interactions, the 6-nonPh CSs demonstrated an equivalent or even higher enantioselectivity compared with the Ph-homo and Ph-hetero CSs.

Stereoselective Synthesis of Enantiopure Oxazolidinones via Biocatalytic Asymmetric Aminohydroxylation of Alkenes

Chiral oxazolidinones are of significance in both medicinal and synthetic chemistry, while preparing these compounds usually involves using expensive starting materials and harsh reaction conditions. Herein, a one-pot biocatalytic cascade process was developed for stereo- and regioselective aminohydroxylation of diverse alkenes by combining styrene monooxygenase and halohydrin dehalogenase, providing an approach to enantiopure oxazolidinones. (Figure presented.).

Novel chiral stationary phases based on 3,5-dimethyl phenylcarbamoylated β-cyclodextrin combining cinchona alkaloid moiety

Novel chiral selectors based on 3,5-dimethyl phenylcarbamoylated β-cyclodextrin connecting quinine (QN) or quinidine (QD) moiety were synthesized and immobilized on silica gel. Their chromatographic performances were investigated by comparing to the 3,5-dimethyl phenylcarbamoylated β-cyclodextrin (β-CD) chiral stationary phase (CSP) and 9-O-(tert-butylcarbamoyl)-QN-based CSP (QN-AX). Fmoc-protected amino acids, chiral drug cloprostenol (which has been successfully employed in veterinary medicine), and neutral chiral analytes were evaluated on CSPs, and the results showed that the novel CSPs characterized as both enantioseparation capabilities of CD-based CSP and QN/QD-based CSPs have broader application range than β-CD-based CSP or QN/QD-based CSPs. It was found that QN/QD moieties play a dominant role in the overall enantioseparation process of Fmoc-amino acids accompanied by the synergistic effect of β-CD moiety, which lead to the different enantioseparation of β-CD-QN-based CSP and β-CD-QD-based CSP. Furthermore, new CSPs retain extraordinary enantioseparation of cyclodextrin-based CSP for some neutral analytes on normal phase and even exhibit better enantioseparation than the corresponding β-CD-based CSP for certain samples.

Asymmetric catalysis with a chiral-at-osmium complex

The first example of a chiral osmium catalyst is reported in which the overall chirality originates exclusively from a stereogenic metal center (metal-centered chirality) with all coordinating ligands being achiral. The non-C2-symmetric chiral-at-metal complex contains two cyclometalated 7-methyl-1,7-phenanthrolinium heterocycles which can be described as two chelating pyridylidene remote N-heterocyclic carbene (rNHC) ligands. The octahedral coordination sphere is completed with one CO and one acetonitrile ligand. A monodentate chiral oxazoline ligand is used as a chiral auxiliary ligand to obtain enantiomerically pure chiral-at-osmium complexes (>99?:?1 e.r.). Finally, it is demonstrated that the developed chiral-at-osmium complex is suitable for ring-closing enantioselective C(sp3)-H aminations, including the first example of catalytic enantioselective cyclizations of azidoformates to chiral 2-oxazolidinones.

Synthesis of Chiral 5-Aryl-2-oxazolidinones via Halohydrin Dehalogenase-Catalyzed Enantio- and Regioselective Ring-Opening of Styrene Oxides

An efficient biocatalytic approach for enantio- and regioselective ring-opening of styrene oxides with cyanate was developed by using the halohydrin dehalogenase HheC from Agrobacterium radiobacter AD1, generating the corresponding chiral 5-aryl-2-oxazoli

Efficient Access to Chiral 2-Oxazolidinones via Ni-Catalyzed Asymmetric Hydrogenation: Scope Study, Mechanistic Explanation, and Origin of Enantioselectivity

Cheap transition metal Ni-catalyzed asymmetric hydrogenation of 2-oxazolones was successfully developed, which provided an efficient synthetic strategy to prepare various chiral 2-oxazolidinones with 95%-99% yields and 97%->99% ee. The gram-scale hydrogenation could be proceeded well with >99% ee in the presence of low catalyst loading (up to 3350 TON). This Ni-catalyzed hydrogenation protocol demonstrated great synthetic utility, and the chiral 2-oxazolidinone product was easily converted to a variety of other important molecules in good yields and without loss of ee values, such as chiral dihydrothiophene-2(3H)-thione, amino alcohol, oxazoline ligand, and allenamide. Moreover, a series of deuterium labeling experiments, control experiments, and DFT calculations were conducted to illustrate a reasonable catalytic mechanism for this Ni-catalyzed asymmetric hydrogenation, which involved a tautomerization between the enamine and its isomer imine and then went through asymmetric 1,2-addition of Ni(II)-H to the preferred imine.

A novel homochiral metal-organic framework with an expanded open cage based on (: R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl: synthesis, X-ray structure and efficient HPLC enantiomer separation

A new homochiral metal-organic framework (MOF) with an expanded open cage based on the (R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl ligand was synthesized and utilized as a novel chiral stationary phase for high-performance liquid chromatography. Twelve racemates including sec-alcohols, sulfoxides, epoxides, lactone, 1,3-dioxolan-2-one, and oxazolidinone were used as analytes for evaluating the separation properties of the chiral-MOF-packed column. Experimentally, the homochiral MOF offered good molecular recognition ability, which suggests good prospects for the application of chiral MOFs as stationary phases for enantioseparation.

Regioselective Ring-Opening of Styrene Oxide Derivatives Using Halohydrin Dehalogenase for Synthesis of 4-Aryloxazolidinones

A biocatalytic approach towards a range of 4-aryloxazolidinones is developed using a halohydrin dehalogenase from Ilumatobacter coccineus (HheG) as biocatalyst. The method is based on the HheG-catalyzed α-position regioselective ring-opening of styrene oxide derivatives with cyanate as a nucleophile, producing the corresponding 4-aryloxazolidinones in moderate to good yields. Synthesis of enantiopure 4-aryloxazolidinones is also achievable using chiral epoxide materials. (Figure presented.).

Synthesis of new C3 symmetric amino acid- and aminoalcohol-containing chiral stationary phases and application to HPLC enantioseparations

We recently reported a new C3-symmetric (R)-phenylglycinol N-1,3,5-benzenetricarboxylic acid-derived chiral high-performance liquid chromatography (HPLC) stationary phase (CSP 1) that demonstrated better results as compared to a previously described N-3,5-dintrobenzoyl (DNB) (R)-phenylglycinol-derived CSP. Over a decade ago, (S)-leucinol, (R)-phenylglycine, and (S)-leucine derivatives were used as the starting materials of 3,5-DNB-based Pirkle-type CSPs for chiral separation. In this study, three new C3-symmetric CSPs (CSP 2, 3, and 4) were prepared by combining the ideas and results mentioned above. Here we describe the synthetic procedures and applications of the new C3-symmetric CSPs (CSP 2–CSP 4).