100018-61-9

Basic information

• Product Name: (R)-2-methyl-2-phenyloxirane
• CAS NO: 100018-61-9
• Molecular Weight: 134.178
• Mol File: 100018-61-9.mol
• Article Data: 106

Chemical Properties

• CAS DataBase Reference: (R)-2-methyl-2-phenyloxirane(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-2-methyl-2-phenyloxirane(100018-61-9)
• EPA Substance Registry System: (R)-2-methyl-2-phenyloxirane(100018-61-9)

Safety Data

• Hazardous Substances Data: 100018-61-9(Hazardous Substances Data)

Upstream product

• 116652-87-0 (2R)-1-((S)-2-methoxymethylpyrrolidino)-2-phenyl-2-propanol 
• 98-83-9 isopropenylbenzene 
• 2085-88-3 2-methyl-2-phenyloxirane 
• 627076-70-4 (R)-2-hydroxy-2-phenylpropyl 4-methylbenzenesulfonate 
• 2406-22-6 (R)-1-phenyl-1,2-ethanediol 
• 70775-39-2 dimethylsulfoxonium methylide 
• 98-86-2 acetophenone 
• 2406-23-7 (R)-ethyl 2-hydroxy-2-phenylpropanoate 
• 15206-55-0 methyl 2-oxo-2-phenylacetate 
• 1603-79-8 phenylglyoxylic acid ethyl ester 
• 131982-01-9 (R)-1-((S)-2-Hydroxy-1-phenyl-ethylsulfanyl)-2-phenyl-propan-2-ol 
• 131981-98-1 2-((S)-2-Hydroxy-1-phenyl-ethylsulfanyl)-1-phenyl-ethanone 
• 116652-85-8 α-((S)-2-methoxymethylpyrrolidino)acetophenone 
• 100-59-4 phenylmagnesium chloride 

Downstream Products

• 34713-70-7 2-Phenylpropanal 
• 37778-99-7 (S)-2-phenyl-1-propanol 
• 1123-85-9 (+)-(R)-2-phenylpropanol 
• 93-53-8 (S)-2-phenyl-propionaldehyde 
• 93-53-8 (R)-2-phenylpropanal 
• 98-83-9 isopropenylbenzene 
• 53777-08-5 (S)-2-phenyl-butan-2-ol 

Relevant articles and documents

A new, facile method to prepare hybrid calcium poly(styrene-phenylvinylphosphonate)-phosphate materials for a superior performance catalyst support

A simple and facile route is developed to synthesize a new type of calcium poly(styrene-phenylvinylphosphosphonate)-phosphate (CaPS-PVPA). Structure analysis reveals that CaPS-PVPA is a layered crystalline mesoporous material and could have potential appl

Stable chiral salen Mn(III) complexes with built-in phase-transfer capability for the asymmetric epoxidation of unfunctionalized olefins using NaOCl as an oxidant

A series of novel chiral salen Mn(III) complexes with inherent phase-transfer capability were prepared by covalent linkage of the limidazolium IL moieties containing various PEG chains with chiral salen ligand at two sides of 5,5′-position. Technologies of characterization well suggested the presence of polyether chain, the IL linker, and the intact active sites in the complexes. The amphipathic nature of the PEG chain allowed the PEG-based catalysts to undergo built-in phase transfer, which in turn increased the reaction rates in water/organic biphasic systems. Enantioselective epoxidation of styrene, α-methylstyrene, indene, 1,2-dihydronaphthalene, 6-cyano-2,2-dimethylchromene, and 6-nitro-2,2-dimethylchromene catalyzed by the complexes with NaOCl gave >99% conversions within 60 min. The enantiomeric excess (ee) for the epoxides was in the range of 68-93%, except for styrene (ee, 35%) and α-methylstyrene (ee, 42%). Furthermore, the PEG-based complexes were stable and could be separated from the reaction mixture by control of the solvent.

An effective strategy for creating asymmetric MOFs for chirality induction: A chiral Zr-based MOF for enantioselective epoxidation

Recently the construction of chiral MOFs (CMOFs) has been very challenging and complex. For the first time, we synthesized a chiral Zr-based MOF with l-tartaric acid by solvent-assisted ligand incorporation (SALI). We show that a CMOF can be postsynthetically generated by a simple method: incorporating chiral carboxylic groups on the achiral NU-1000. The post-synthesized chiral NU-1000 was used as an asymmetric support for producing a chiral catalyst with molybdenum catalytic active centers as Lewis acid sites. Enantioselective epoxidation of various prochiral alkens to epoxids by using [C-NU-1000-Mo] is comparable to that using other asymmetric homogeneous and heterogeneous catalysts, along with high enantiomeric excess and selectivity to epoxide (up to 100%). The CMOF could be reused in the styrene oxidation after five cycles without substantial deterioration in the CMOF crystallinity or catalytic performance.

Enhanced enantioselective oxidation of olefins catalyzed by Mn-porphyrin immobilized on graphene oxide

An efficient enantioselective heterogeneous catalyst, GO-[Mn(TPyP)tart], was prepared by covalent attachment of Mn(III) complex of H2TPyP via the propyl linkage to graphene oxide (GO) nanosheet and using chiral tartrate counter ion. The catalyst was characterized by Fourier transform infrared (FT-IR), diffuse reflectance ultraviolet–visible (DR UV–Vis) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and thermogravimetric analysis (TGA). The graphene-supported Mn-porphyrin showed higher activity for the enantioselective epoxidation of unfunctionalized olefins with molecular oxygen in the presence of isobutyraldehyde. It could be recovered easily and reused in asymmetric oxidation of styrene precursor in a five-step sequence without any considerable loss of its catalytic activity and selectivity. The obtained optically epoxide selectivities were achieved in 86% to 100%.

Stereoselective benzylic hydroxylation of alkylbenzenes and epoxidation of styrene derivatives catalyzed by the peroxygenase of Agrocybe aegerita

Here we report on the stereoselective benzylic hydroxylation and C1-C2 epoxidation of alkylbenzenes and styrene derivatives, respectively, by a heme-thiolate peroxygenase (EC 1.11.2.1) from the fungus Agrocybe aegerita. Benzylic hydroxylation led exclusively to the (R)-1-phenylalkanols. For (R)-1-phenylethanol, (R)-1-phenylpropanol and (R)-1-tetralol, the ee reached >99%. For longer chain lengths, the enantiomeric excesses (ee) and total turnover numbers (TTN) decreased while the number of by-products, e.g. 1-phenylketones, increased. Epoxidation of straight chain and cyclic styrene derivatives gave a heterogeneous picture and resulted in moderate to excellent ee values and TTN: e.g., in the case of (1R,2S)-cis-β-methylstyrene oxide formation, an ee >99% and a TTN of 110000 was achieved. Hydroxylation and epoxidation were true peroxygenations, which was demonstrated by the incorporation of 18O from H218O2 into the products. The use of fed-batch devices and varying feeding strategies for the substrate and co-substrate turned out to be a suitable approach to optimize peroxygenase catalysis.

A series of crystalline organic polymer-inorganic hybrid material zinc-phosphonate-phosphates synthesized in the presence of templates for superior performance catalyst support

New types of organic copolymer-inorganic hybrid material zinc-phosphonate-phosphates are prepared with amines as templates. Notably, crystalline samples are obtained not with traditional methods but with simple reactions. Moreover, the samples are provide

Oxiranyl anion-mediated synthesis of highly enantiomerically enriched styrene oxide derivatives

(Matrix presented) The stereospecific α-lithiation of optically active styrene oxides and the trapping reaction of the corresponding highly reactive intermediates with electrophiles to produce optically active styrene oxide derivatives are described. This methodology has been applied to the synthesis of an optically active oral antifungal agent of industrial interest.

An achiral manganese salen catalyst encapsulated in a peptidic phosphonate homochiral solid for the enantioselective formation of diols by consecutive epoxidation and hydration reactions

An insoluble, porous, amorphous, homochiral material based on a polypeptide titanium-phosphonate scaffold with an encapsulated achiral Mn III-salen was prepared and characterized. Consecutive epoxidation and hydration of styrene and its derivatives by aqueous hypochlorite in THF showed the highly enantioselective (>99%) formation of styrene diol derivatives.

Reusable chiral salen Mn(III) complexes with phase transfer capability efficiently catalyze the asymmetric epoxidation of unfunctionalized olefins with NaClO

A series of chiral salen Mn(III) polymers with build-in phase transfer capability was prepared by bridging the chiral salen Mn(III) units with polyethylene glycol (PEG)-based di-imidazolium ionic liquid (IL) side by side. Technologies of characterization

Enantioselective epoxidation of unfunctionalised olefins catalyzed by Mn(salen) complexes immobilized in porous materials via phenyl sulfonic group

Heterogeneous chiral Mn(salen) catalysts axially immobilized on mesoporous materials via phenyl sulfonic groups result in remarkably higher ee values (up to 95%) for asymmetric epoxidation of unfunctionalised olefins. The Royal Society of Chemistry 2005.

A new heterogeneous chiral (salen)manganese(III) system for enantioselective epoxidation of non-functionalized olefins

This communication describes the design and application of a novel catalytic epoxidation system derived from the initial immobilization of a homogeneous sulfonato (salen)Mn(III) complex on two solid carriers (silica gel and siliceous earth) and subsequent dispersion of the supported manganese complexes into ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMImPF6) and 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) for recycling. The performance of chiral (salen)Mn(III) system in enantioselective epoxidation of olefins was investigated systematically. Even higher enantioselectivity than that of the homogeneous counterpart was obtained with similar catalytic activity. In particular, the best catalytic result is that the combination of the silica gel-supported (salen)Mn(III) catalyst and BMImPF6 affords 97-100% ee for epoxidation of α-methylstyrene, and high ee values were retained even after three cycles.

Construction of an Asymmetric Porphyrinic Zirconium Metal-Organic Framework through Ionic Postchiral Modification

Herein, one kind of neutral chiral zirconium metal-organic framework (Zr-MOF) was reported from the porphyrinic MOF (PMOF) family with a metallolinker (MnIII-porphyrin) as the achiral polytopic linker [free base tetrakis(4-carboxyphenyl)porphyrin] and chiral anions. Achiral Zr-MOF was chiralized through the exchange of primitive anions with new chiral organic anions (postsynthetic exchange). This chiral functional porphyrinic MOF (CPMOF) was characterized by several techniques such as powder X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, 1H NMR, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller measurements. In the resulting structure, there are two active metal sites as Lewis acid centers (Zr and Mn) and chiral species as Br?nsted acid sites along with their cooperation as nucleophiles. This CPMOF shows considerable bimodal porosity with high surface area and stability. Additionally, its ability was investigated in asymmetric catalyses of prochiral substrates. Interactions between framework chiral species and prochiral substrates have large impacts on the catalytic ability and chirality induction. This chiral catalyst proceeded asymmetric epoxidation and CO2 fixation reactions at lower pressure with high enantioselectivity due to Lewis acids and chiral auxiliary nucleophiles without significant loss of activity up to the sixth step of consecutive cycles of reusability. Observations revealed that chiralization of Zr-MOF could happen by a succinct strategy that can be a convenient method to design chiral MOFs.

Enhanced Turnover for the P450 119 Peroxygenase-Catalyzed Asymmetric Epoxidation of Styrenes by Random Mutagenesis

A randomized library is constructed based on pET30a-CYP119-T214V plasmid. This library of random mutants of CYP119-T214V was screened by means of the reduced CO difference spectra and epoxidation of styrene. By using directed evolution, a new CYP119 quadr

Collaborative effect of Mn-porphyrin and mesoporous SBA-15 in the enantioselective epoxidation of olefins with oxygen

The rational design of heterogeneous, low cost transition metal complexes that can catalyze olefin with high enantioselectivity and activity has been a challenging goal for the synthetic chemist. In this study a chiral ion pair strategy was used for the synthesis of a biomimetic efficient manganese-tetrapyridylporphyrin (H2TPyP) catalyst for the asymmetric epoxidation of olefins with O2. Complex Mn-TPyP was covalently linked to mesoporous SBA-15 in heme-type environments and its counter ion was replaced by L-tartrate anion (SBA15-[Mn(TPyP)TA]). Chiral and achiral homogeneous analogous of Mn-TPyP were also prepared. The Mn-porphyrin confined in nanoreactors of SBA-15 exhibited enhanced activity (TOF = 652 h?1) and enantiomeric excess (ee 93%) compared with the value obtained when the same chiral catalyst functioned in homogeneous solution (TOF 97 h?1 and ee 83%) in the oxidation of 1-decene with O2/isobutyraldehyde. The high specific surface area, uniformly sized pore channels and site isolated active centers of the catalyst may contribute to the high activity and enantioselectivity. SBA15-[Mn(TPyP)TA] was structurally stable and could be recycled for repeated use. Total turnover number in the oxidation of styrene after five cycles was 47,400 with 86% epoxide selectivity and ee 86%.

A magnetically recyclable Fe3O4@SiO2/Mn(III) chiral salen complex as a highly selective and versatile heterogeneous nanocatalyst for the oxidation of olefins and sulfides

In this study, a new magnetically recoverable heterogeneous Mn(iii) nanocatalyst (MHMC) was developed by covalent grafting of a homogeneous chiral Mn(iii) salen complex (HMC) onto the surface of a Fe3O4/SiO2 core-shell. The structural and chemical nature of MHMC was characterized by different techniques. The catalytic activity of the MHMC and comparison with its homogeneous analogue were studied for the enantioselective epoxidation of various alkenes to epoxide compounds using tert-butyl hydroperoxide (TBHP) as an oxidant. The MHMC showed higher enantioselectivity and comparable catalytic reactivity to its homogeneous analogue with benefits such as facile recovery and recycling of the heterogeneous catalyst. The results showed that a higher enantioselectivity and yield were observed in the presence of N-methylmorpholine N-oxide (NMNO). The catalytic activity of this complex was also tested in the oxidation of sulfides using aqueous 30% H2O2 in excellent yields. The catalyst was reused for several runs without significant loss in activity and selectivity.

Enantioselective epoxidation of unfunctionalized olefins by Jacobsen's catalyst immobilized on amino-modified ZnPS-PVPA

Catalytic asymmetric epoxidation of alkenes is a powerful method for the synthesis of chiral organic compounds. A recyclable chiral Jacobsen's catalyst immobilized on ZnPS-PVPA on diamines gave high catalytic activity (conversion > 99%, ee > 99%) in the asymmetric epoxidations of unfunctionalized olefins. The synergistic effect of the support ZnPS-PVPA and the linkage as well as chiral salen Mn center contributed to the chirality of the product. The stability (recycled nine times) and the ease of use in large scale reactions (200 times scale) indicated a catalyst useful for industrial use.

A novel layered organic polymer-inorganic hybrid zinc poly (styrene-phenylvinylphosphonate)-phosphate immobilized chiral salen Mn(III) catalyst large-scale asymmetric epoxidation of unfunctionalized olefins

A novel layered organic polymer-inorganic hybrid zinc poly (styrene-phenylvinylphosphonate)-phosphate (ZnPS-PVPA) has been synthesized under mild conditions and diphenol-modified ZnPS-PVPA was used to successfully immobilize the chiral salen Mn(III) by axial coordination. The obtained heterogeneous chiral catalysts exhibited excellent activities and enantioselectivities using sodium periodate as an oxidant for asymmetric epoxidation of unfunctionalized olefins, especially for the epoxidation of α-methylstyrene (conversion: up to 97%; ee: exceed 99%). Moreover, these synthesized catalysts were relatively stable and could be expediently separated from the reaction system, and could be recycled at least ten times without obvious loss of activity and enantioselectivity. These novel catalysts could be efficiently used in large-scale reactions with the enantioselectivity being maintained at the same level, which offer a great possibility for application in industry.

Heterogeneous Jacobsen's catalyst on alkoxyl-modified zirconium poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA) for asymmetric epoxidation

Chiral Jacobsen's catalysts grafted onto alkoxyl-modified ZPS-PVPA exhibit excellent activities (conv%, up to 96; sele%, up to 96; ee%, up to >99) in the asymmetric epoxidations of unfunctionalized olefins. The superior stabilities and the comfortable dis

An improved catalytic system for recycling OsO4 and chiral ligands in the asymmetric dihydroxylation of olefins

A recyclable catalytic system for the asymmetric dihydroxylation of olefins was developed by using a mono-quaternized bis-cinchona alkaloid ligand 3 and OsO4 combined with PEG or an ionic liquid. Both the catalytic components could be recovered and reused in five consecutive reactions without any additional OsO4 or ligand. The catalytic system is effective in the AD reactions of seven olefins.

Grafting of a chiral Mn(iii) complex on graphene oxide nanosheets and its catalytic activity for alkene epoxidation

A chiral Mn(iii) complex supported by a covalent grafting method on modified graphene oxide was synthesized using 3-chloropropyltrimethoxysilane as a reactive surface modifier. The heterogeneous catalyst was characterized by X-ray diffraction, Fourier transform infrared spectra, thermogravimetric analysis, ultraviolet-visible spectra, nitrogen adsorption-desorption isotherms, transmission electron microscopy and atomic absorption spectroscopy. The catalytic potential of the heterogeneous catalyst and comparison with its homogeneous counterpart were studied for enantioselective epoxidation of various alkenes using m-chloroperbenzoic acid as an oxidant and it showed high selectivity and comparable catalytic reactivity with its homogeneous analogue. In addition, higher enantioselectivity and higher yield were observed in the presence of 4-methylmorpholine N-oxide and pyridine N-oxide, respectively. The catalyst was reused for several runs without significant loss of activity and selectivity.

Monodisperse crosslinked pHEMA particle-supported chiral Mn(III)salen catalyst for asymmetric epoxidation of olefin

Monodisperse crosslinked poly(hydroxyethyl methacrylate) particles (pHEMA) were synthesized for immobilization of the chiral Mn(III)salen homogeneous catalyst by axial coordination. The pHEMA-Mn(III)salen catalyst was subsequently characterized by FT-IR, UV and scanning electron microscopy. The results showed that, the heterogeneous Mn(III)salen catalysts also exhibited high activity and enantioselectivity compared to the homogeneous catalyst for the disubstituted cyclic indene and 6-cyano-2,2-dimethylchromene. Moreover, the catalysts were easily separated from the reaction systems and could be renewed several times without significant loss of catalytic activity. Meanwhile, the enantiomeric excess (ee) value remained at 80% in the eighth cycle. The pHEMA support, immobilized by Mn(III)salen, probably acted as a mediator of the reaction between the substrate and the oxidant, and enhanced the stability of the Mn(III)salen compound. Copyright

Enantioselective, Lewis Base-Catalyzed Carbosulfenylation of Alkenylboronates by 1,2-Boronate Migration

A catalytic, enantioselective method for the preparation of chiral, non-racemic, alkylboronic esters bearing two vicinal stereogenic centers is described. The reaction proceeds via a 1,2-migration of a zwitterionic thiiranium-boronate complex to give excl

Studies on the synthesis of a chiral salen Mn (III) complex immobilised onto zirconium aminophosphonates and catalytic asymmetric epoxidation of α-methylstyrene

A chiral salen Mn (III) complex has been immobilised onto zirconium aminophosphonates by axial coordination with different linkage arm lengths (CH2)n (n = 2-6), to give a series of heterogeneous catalysts. The catalysts exhibited good to excellent catalytic efficiency in the asymmetric epoxidation of α-methylstyrene. One heterogeneous catalyst, with n = 6, gave higher catalytic properties than the original chiral salen Mn (III) complex in the NaClO/PPNO system. It can be easily recovered and reused several times without significant loss of activity.

A Robust Metal-Metalloporphyrin Framework Based upon a Secondary Building Unit of Infinite Nickel Oxide Chain

Herein we report the construction of a robust metal-metalloporphyrin framework that is based upon a rare secondary building unit of infinite nickel oxide chain. The constructed MMPF-20 exhibits permanent porosity and selective adsorption of CO2 over CH4 as well as demonstrates interesting catalytic performances in the context of olefin epoxidation.

Enantioselective aerobic oxidation of olefins by magnetite nanoparticles at room temperature: A chiral carboxylic acid strategy

Asymmetric oxidations of organic compounds are limited in their synthetic scope and by practical factors, such as the use of complex catalyst synthesis. A simple and cheap nanostructured catalyst system comprising magnetite nanoparticles stabilized by l-(+)-tartaric acid (Fe3O4/tart-NPs) was successfully synthesized in diethylene glycol. The catalyst was characterized by FT-IR, TGA, ICP-AES, XRPD, SEM and dynamic light scattering (DLS). The catalytic activity of Fe3O4/tart-NPs dispersion in acetonitrile in the presence of isobutyraldehyde was studied in selective aerobic oxidation of olefins to form asymmetric epoxide, an important intermediate for the synthesis of biologically active compounds. In addition, the magnetically recoverable nanocatalyst Fe3O4/tart-NPs can be conveniently separated and recovered from the reaction system by applying an external magnetic field and reused for five cycles without the loss of activity after each cycle. These results demonstrate that the heterogeneous nanocatalysts possess potential applications for green and sustainable development. As synthesized nanoparticles of Fe3O4/tart-NPs are cheap and easy to synthesize asymmetric catalysts which were prepared without the involvement of difficult and cumbersome procedures for the synthesis of complicated asymmetric ligands. Possible reaction mechanisms were outlined.

Chiral porous poly(ionic liquid)s: Facile one-pot, one-step synthesis and efficient heterogeneous catalysts for asymmetric epoxidation of olefins

Ionic liquids are potential media/solvents for asymmetric synthesis when combined with chiral catalysts, while most reported catalysts are homogenous, making them difficult to separate from the reaction systems. Herein, chiral porous poly(ionic liquid)s (