134356-74-4

Usage

Uses

Used in Pharmaceutical Industry:
(S)-(4-Fluorophenyl)oxirane is used as a key intermediate in the synthesis of optically active molecules. These molecules are crucial for the development of pharmaceuticals that target monoamine transporters, such as dopamine, serotonin, and norepinephrine. The chiral nature of (S)-(4-Fluorophenyl)oxirane allows for the creation of enantiomerically pure drugs, which can have different biological activities and reduce potential side effects.
Used in Organic Synthesis:
(S)-(4-Fluorophenyl)oxirane is used as an epoxide reagent in various organic synthesis processes. Its reactivity allows for the formation of new carbon-carbon bonds, making it a valuable building block for the creation of complex organic molecules. This versatility makes it a popular choice for chemists working on the development of new compounds with potential applications in various industries, including pharmaceuticals, agrochemicals, and materials science.

InChI:InChI=1/C8H7FO/c9-7-3-1-6(2-4-7)8-5-10-8/h1-4,8H,5H2/t8-/m1/s1

Upstream product

• 459-57-4 4-fluorobenzaldehyde 
• 456-04-2 2-Chloro-4'-fluoroacetophenone 
• 112022-81-8 (S)-1-methyl-3,3-diphenyl-hexahydropyrrolo[1,2-c][1,3,2]oxazaborole 
• 405-99-2 para-fluorostyrene 
• 134295-34-4 S-(+)-2-chloro-1-(4-fluorophenyl)ethanol acetate 
• 126534-42-7 (S)-1-chloro-2-hydroxy-2-(p-fluorophenyl)ethane 
• 403-42-9 1-(4-fluorophenyl)ethanone 
• 61592-48-1 2-Chloro-1-(4-fluorophenyl)ethanol 
• 18511-62-1 4-fluorostyrene oxide 
• 53617-32-6 2-bromo-1-(4-fluorophenyl)ethan-1-ol 
• 593-71-5 Chloroiodomethane 
• 1030268-21-3 trimethylsulfonium iodide 
• 5347-82-0 dimesylamine 
• 2181-42-2 trimethylsulphonium iodide 

Downstream Products

• 403-41-8 1-(4-Fluorophenyl)ethanol 
• 7589-27-7 2-(4-Fluorophenyl)ethanol 
• 18511-62-1 (2S)-2-(4-fluorophenyl)oxirane 
• 213479-90-4 (S)-(+)-1-(4-fluorophenyl)-1,2-ethanediol 
• 179694-35-0 (R)-(-)-1-(4-fluorophenyl)-1,2-ethanediol 
• 18511-62-1 R-(-)-2-(4-fluorophenyl)oxirane 
• 866886-40-0 2-azido-2-(4-fluorophenyl)ethan-1-ol 
• 140373-17-7 α-hydroxymethyl-4-fluorobenzylamine 
• 823786-71-6 methanesulfonic acid 2-(4-fluoro-phenyl)-2-phenoxycarbonylamino-ethyl ester 
• 823786-80-7 1-(2,3-dihydro-1H-indole-5-sulfonyl)-4-(4-fluoro-phenyl)-imidazolidin-2-one 
• 144872-26-4 4-[N-[2-(4-Fluorophenyl)-2-hydroxyethyl]-N-methylamino]-1-(4-nitrophenyl)piperidine 
• 1736-67-0 4-fluorophenylacetaldehyde 
• 459-57-4 4-fluorobenzaldehyde 
• 18511-64-3 rac-2-(4-fluorophenyl)thiirane 

Relevant academic research and scientific papers

Asymmetric Epoxidation of Olefins Catalyzed by Substituted Aminobenzimidazole Manganese Complexes Derived from L-Proline

A family of manganese complexes [Mn(Rpeb)(OTf)2] (peb=1-(1-ethyl-1H-benzo[d]imidazol-2-yl)-N-((1-((1-ethyl-1H-benzo[d]imidazol-2-yl)methyl) pyrrolidin-2-yl)methyl)-N-methylmethanamine)) derived from L-proline has been synthesized and characterized, where R refers to the group at the diamine backbone. X-ray crystallographic analyses indicate that all the manganese complexes [Mn(Rpeb)(OTf)2] exhibit cis-α topology. These types of complexes are shown to catalyze the asymmetric epoxidation of olefins employing H2O2 as a terminal oxidant with up to 96% ee. Obviously, the R group of the diamine backbone can influence the catalytic activity and enantioselectivity in the asymmetric epoxidation of olefins. In particular, Mn(i-Prpeb)(OTf)2 bearing an isopropyl arm, cannot catalyze the epoxidation reaction with H2O2 as the oxidant. However, when PhI(OAc)2 is used as the oxidant instead, all the manganese complexes including Mn(i-Prpeb)(OTf)2 can promote the epoxidation reactions efficiently. Taken together, these results indicate that isopropyl substitution on the Rpeb ligand inhibits the formation of active Mn(V)-oxo species in the H2O2/carboxylic acid system via an acid-assisted pathway.

Synthesis of new chiral Mn(iii)-salen complexes as recoverable and reusable homogeneous catalysts for the asymmetric epoxidation of styrenes and chromenes

New chiral Mn(iii)-salen complexes 1a-e and 2a-e were synthesized from the reaction of C2-symmetric chiral salen ligands and Mn(CH3COO)2·4H2O under an inert atmosphere followed by aerobic oxidation. These complexes were obtained in 91-96% yields and characterized by HRMS, FT-IR, UV-visible spectroscopy, TGA, and elemental analysis. The chiral Mn(iii)-salen complexes 1a-e and 2a-e were evaluated in the asymmetric epoxidation of styrene using NaOCl as an oxidant in ethyl acetate as a green solvent. The chiral Mn(iii)-salen complexes 1b and 2b (2 mol%) catalyzed the asymmetric epoxidation of substituted styrenes and chromenes to afford the corresponding epoxides in 95-98% yields with 29-88% ee's. The catalysts 1b and 2b were recovered and reused for up to 2 and 3 runs, respectively, in the asymmetric epoxidation of styrene, and the yield of styrene oxide gradually decreased but the ee was consistent.

Structure-Guided Regulation in the Enantioselectivity of an Epoxide Hydrolase to Produce Enantiomeric Monosubstituted Epoxides and Vicinal Diols via Kinetic Resolution

Structure-guided microtuning of an Aspergillus usamii epoxide hydrolase was executed. One mutant, A214C/A250I, displayed a 12.6-fold enhanced enantiomeric ratio (E = 202) toward rac-styrene oxide, achieving its nearly perfect kinetic resolution at 0.8 M in pure water or 1.6 M in n-hexanol/water. Several other beneficial mutants also displayed significantly improved E values, offering promising biocatalysts to access 19 structurally diverse chiral monosubstituted epoxides (97.1 - ≥ 99% ees) and vicinal diols (56.2-98.0% eep) with high yields.

Effect of the Ligand Backbone on the Reactivity and Mechanistic Paradigm of Non-Heme Iron(IV)-Oxo during Olefin Epoxidation

The oxygen atom transfer (OAT) reactivity of the non-heme [FeIV(2PyN2Q)(O)]2+ (2) containing the sterically bulky quinoline-pyridine pentadentate ligand (2PyN2Q) has been thoroughly studied with different olefins. The ferryl-oxo complex 2 shows excellent OAT reactivity during epoxidations. The steric encumbrance and electronic effect of the ligand influence the mechanistic shuttle between OAT pathway I and isomerization pathway II (during the reaction stereo pure olefins), resulting in a mixture of cis-trans epoxide products. In contrast, the sterically less hindered and electronically different [FeIV(N4Py)(O)]2+ (1) provides only cis-stilbene epoxide. A Hammett study suggests the role of dominant inductive electronic along with minor resonance effect during electron transfer from olefin to 2 in the rate-limiting step. Additionally, a computational study supports the involvement of stepwise pathways during olefin epoxidation. The ferryl bend due to the bulkier ligand incorporation leads to destabilization of both (Formula presented.) and (Formula presented.) orbitals, leading to a very small quintet–triplet gap and enhanced reactivity for 2 compared to 1. Thus, the present study unveils the role of steric and electronic effects of the ligand towards mechanistic modification during olefin epoxidation.

Synthesis of a light-harvesting ruthenium porphyrin complex substituted with BODIPY units. Implications for visible light-promoted catalytic oxidations

A light-harvesting ruthenium porphyrin substituted covalently with four boron-dipyrrin (BODIPY) moieties has been synthesized and studied. The resulting complex showed an efficient decarbonylation reaction predominantly due to a photo-induced energy transfer process. Chemical oxidation of the ruthenium(ii) BODIPY-porphyrin afforded a high-energytrans-dioxoruthenium(vi) species that is one order of magnitude more reactive towards alkene oxidation than those analogues supported by conventional porphyrins. In the presence of visible light, the ruthenium(ii) BODIPY-porphyrin displayed remarkable catalytic activity toward sulfide oxidation and alkene epoxidation using iodobenzene diacetate [PhI(OAc)2] and 2,6-dichloropyridineN-oxide (Cl2pyNO) as terminal oxidants, respectively. The findings in this work highlight that porphyrin-BODIPY conjugated metal complexes are potentially useful for visible light-promoted catalytic oxidations.

Mechanochemical Synthesis of 1,2-Diketoindolizine Derivatives from Indolizines and Epoxides Using Piezoelectric Materials

A simple and efficient mechanochemical-induced approach for the synthesis of 1,2-diketoindolizine derivatives has been developed. BaTiO3 was used as the piezoelectric material in this transformation. This method features no usage of solvent, simple experimental operation, scalable potential, and high conversion efficiency, which make it attractive and practical.

Diastereoselective Alkene Hydroesterification Enabling the Synthesis of Chiral Fused Bicyclic Lactones

Palladium-catalysed diastereoselective hydroesterification of alkenes assisted by the coordinative hydroxyl group in the substrate afforded a variety of chiral γ-butyrolactones bearing two stereocenters. Employing the carbonylation-lactonization products as the key intermediates, the route from the alkenes with single chiral center to chiral THF-fused bicyclic γ-lactones containing three stereocenters was developed.

Asymmetric azidohydroxylation of styrene derivatives mediated by a biomimetic styrene monooxygenase enzymatic cascade

Enantioenriched azido alcohols are precursors for valuable chiral aziridines and 1,2-amino alcohols, however their chiral substituted analogues are difficult to access. We established a cascade for the asymmetric azidohydroxylation of styrene derivatives leading to chiral substituted 1,2-azido alcohols via enzymatic asymmetric epoxidation, followed by regioselective azidolysis, affording the azido alcohols with up to two contiguous stereogenic centers. A newly isolated two-component flavoprotein styrene monooxygenase StyA proved to be highly selective for epoxidation with a nicotinamide coenzyme biomimetic as a practical reductant. Coupled with azide as a nucleophile for regioselective ring opening, this chemo-enzymatic cascade produced highly enantioenriched aromatic α-azido alcohols with up to >99% conversion. A bi-enzymatic counterpart with halohydrin dehalogenase-catalyzed azidolysis afforded the alternative β-azido alcohol isomers with up to 94% diastereomeric excess. We anticipate our biocatalytic cascade to be a starting point for more practical production of these chiral compounds with two-component flavoprotein monooxygenases.

Halohydrin dehalogenase-catalysed synthesis of fluorinated aromatic chiral building blocks

Kinetic resolution of a series of fluorinated styrene oxide derivatives was studied using halohydrin dehalogenase. A mutant HheC-W249P catalysed nucleophilic ring-opening with azide and cyanide ions with excellent enantioselectivity (E-values up to >200), which gives access to various enantiopure β-substituted alcohols and epoxides. It was found that the enzyme tolerates substrates in concentrations over 50 mM. However, different side reactions were observed at elevated concentrations and with prolonged reaction time. The biocatalytic azidolysis and cyanolysis of racemic 4-trifluoromethylstyrene oxide were performed on preparative scale, affording (R)-2-azido-1-(4-trifluoromethyl-phenyl)-ethanol in 38% yield and 97% ee, and (S)-3-hydroxy-3-(4-trifluoromethyl-phenyl)-propionitrile in 30% yield and 98% ee.

Aerobic epoxidation of styrene over Zr-based metal-organic framework encapsulated transition metal substituted phosphomolybdic acid

Catalytic epoxidation of styrene with molecular oxygen is regarded as an eco-friendly alternative to producing industrially important chemical of styrene oxide (STO). Recent efforts have been focused on developing highly active and stable heterogeneous catalysts with high STO selectivity for the aerobic epoxidation of styrene. Herein, a series of transition metal monosubstituted heteropolyacid compounds (TM-HPAs), such as Fe, Co, Ni or Cu-monosubstituted HPA, were encapsulated in UiO-66 frameworks (denoted as TM-HPA@UiO-66) by direct solvothermal method, and their catalytic properties were investigated for the aerobic epoxidation of styrene with aldehydes as co-reductants. Among them, Co-HPA@UiO-66 showed relatively high catalytic activity, stability and epoxidation selectivity at very mild conditions (313 K, ambient pressure), that can achieve 82 % selectivity to STO under a styrene conversion of 96 % with air as oxidant and pivalaldehyde (PIA) as co-reductant. In addition, the hybrid composite catalyst can also efficiently catalyze the aerobic epoxidation of a variety of styrene derivatives. The monosubstituted Co atoms in Co-HPA@UiO-66 are the main active sites for the aerobic epoxidation of styrene with O2/PIA, which can efficiently converting styrene to the corresponding epoxide through the activation of the in-situ generated acylperoxy radical intermediate.