184488-93-5

Upstream product

• 5989-27-5 D-limonene 
• 138-86-3 limonene. 
• 1025858-03-0 2-((1R,3S,4S)-3-Bromo-4-methoxy-4-methyl-cyclohexyl)-2-methyl-oxirane 

Downstream Products

• 76738-75-5 α-bisabolol 
• 23178-88-3 (2R)-6-methyl-2-[(1R)-4-methylcyclohex-3-en-1-yl]hept-5-en-2-ol 
• 28098-67-1 (R)-2-methyl-2-((R)-4-methylcyclohex-3-enyl)oxirane 
• 28098-68-2 (S)-2-methyl-2-((R)-4-methylcyclohex-3-enyl)oxirane 
• 96-08-2 R-(+)-limonene diepoxide 
• 200723-09-7 (4R,8Ξ)-p-menth-1-ene-8,9-diol 

Relevant academic research and scientific papers

Interaction of a chirally functionalised porphyrin derivative with chiral micellar aggregates. Construction of a system with stereoselective cytochrome-P450 biomimetic activity

The inclusion behaviour of porphyrin derivative manganese [5-(4-(carboxyphenyl-(N-L-proline)))-10-15-20-triphenylporphyrinyl] chloride 1MnCl in micellar aggregates of sodium N-dodecanoyl-L-prolinate L-SDP and of sodium dodecylsulfate SDS has been studied by means of several spectroscopic techniques. The catalytic activity in the epoxidation reaction of some test chiral olefins has been also investigated. Comparison with the case of the related manganese[5-(4-carboxyphenyl)-10-15-20-triphenylporphyrinyl] chloride 2MnCl, gave evidence that suggests the presence of a chiral functionality on the periphery of porphyrin macrocycles affects their aggregation mode within the biomembrane models. This results in the modulation of their stereoselective Cytochrome P450 biomimetic activity.

Molybdenum-doped epoxy resins as catalysts for the epoxidation of alkenes

Epoxy resins were polymerised using molybdenum ethoxide and 2-ethylhexanoate as polymerisation initiators. The thermosets thus obtained are useful epoxidation catalysts for a variety of alkenes, including propene with tert-butyl hydroperoxide as an oxidant. To investigate the long-term performance of these resins, they were used repeatedly in up to 120 reactions without any reconditioning. Compared with other catalyst systems based on organic polymers, they reveal unprecedented long-term activities over periods of months so that catalyst lifetimes of years can be expected. Di-, tri-, tetra- and oligofunctional epoxy resin monomers were used and compared. The catalytic performance of the thermosets strongly depends on the resin type and the polymerisation initiator. Promising results were obtained with monomers bearing 3 or 4 glycidyl groups in combination with Mo(OEt)5 as an initiator. Metal leaching, determined by sensitive atomic spectroscopic techniques, is extremely low. Inorganic-organic hybrid catalysts can be easily prepared by adding inorganic components such as silicagel to the liquid resins, followed by polymerisation.

A cyclodextrin-modified ketoester for stereoselective epoxidation of alkenes

A β-cyclodextrin-modified ketoester 2 was prepared by covalent attachment of a reactive ketone moiety to β-cyclodextrin. Treatment of 2 with Oxone as terminal oxidant would produce CD-substituted dioxirane, which can effect stereoselective alkene epoxidation. The 2-mediated (S)-α-terpineol epoxidations proceeded to give terpineol oxides in high yields, and the stereoselectivities (i.e., cis-/trans-epoxide ratio) decreased from 2.5:1 to 1:1.2 with increasing steric bulkiness of the terpenes. This steric-dependent stereoselectivity can be understood based on different binding geometries of the 2/terpene inclusion complexes according to the 1H NMR titration and 2D ROESY experiments. Enantioselective epoxidation of styrenes has also been achieved with 2 as catalyst (20-50 mol %) in aqueous acetonitrile solution, and up to 40% ee was obtained in 4-chlorostyrene epoxidation at 0 °C. Similar enantioselectivities were also obtained for the 2-mediated epoxidation of 1,2-dihydronaphthalene (37% ee), 4-chlorostyrene (36% ee), and trans-stilbene (31% ee).

Highly selective and efficient olefin epoxidation with pure inorganic-ligand supported iron catalysts

Over the past two decades, there have been major developments in the transition iron-catalyzed selective oxidation of alkenes to epoxides; a common structure found in drug, isolated natural products, and fine chemicals. Many of these approaches have enabled highly efficient and selective epoxidation of alkenes via the design of specialized ligands, which facilitates to control the activity and selectivity of the reactions catalyzed by iron atom. Herein, we report the development of the olefin epoxidation with inorganic-ligand supported iron-catalysts using 30% H2O2 as an oxidant, and the mechanism is similar to iron-porphyrin type. With the catalyst 1, (NH4)3[FeMo6O18(OH)6], various aromatic and aliphatic alkenes were successfully transformed into the corresponding epoxides with excellent yields as well as chemo- and stereo-selectivity. This catalytic system possesses the advantages of being able to avoid the use of expensive, toxic, air/moisture sensitive and commercially unavailable organic ligands. The generality of this methodology is simple to operate and exhibits high catalytic activity as well as excellent stability, which gives it the potential to be used on an industrial scale, and maybe opens a way for the catalytic oxidation reaction via inorganic-ligand coordinated iron catalysis.

Tungstenocene-grafted silica catalysts for the selective epoxidation of alkenes

Tungstenocene(IV) dichloride was successfully deposited and grafted on the surface of a commercially-available non-ordered silica support via either a liquid-phase or a dry impregnation approach. After a high-temperature calcination step, two W(VI)-grafted silica catalysts, with a metal loading around 1.2–1.7 wt.%, were obtained. They were fully characterized by physisorption and spectroscopic techniques, which evidenced well-dispersed tungsten oxide polyoxo cluster sites, for the catalyst prepared via liquid-phase grafting, and evenly dispersed larger monoclinic tungsten(VI) oxide aggregates, for the catalyst prepared via dry impregnation, respectively. Both W/SiO2 solids showed moderate to good conversion values in the epoxidation of (R)-(+)-limonene and methyl oleate (up to 68%), in the presence of aqueous hydrogen peroxide, with good selectivity to the desired epoxides (63% and 78%, respectively). The heterogeneous character of the most interesting W/SiO2 catalyst prepared via dry impregnation was confirmed by a hot centrifugation test and by an extended recovery and reuse of the solid in six catalytic runs.

An Organotin Vanadate with Sodalite Topology and Catalytic Versatility in Oxidative Transformations

The new coordination polymer formulated as [Et3SnVO3] (1) has been synthesized and shown by a combined single-crystal and synchrotron powder X-ray diffraction structural analysis, supported by solid-state NMR, to possess a three-dimensional network structure with the sodalite topology, formed by tetravanadate polyanions, [V4O12]4?, that are linked by Et3Sn+ spacers. The catalytic versatility of compound 1 for liquid phase organic reactions was demonstrated by applying it for the epoxidation of olefins, the oxidative dehydrogenation of alcohols, and the oxidation of benzyl alcohol to benzaldehyde and benzoic acid, using tert-butyl hydroperoxide (TBHP) as oxidant. Compound 1 acts a solid reservoir for soluble, catalytically active species, which promote high selectivities to the epoxide and carbonyl (aldehyde/ketone/acid) products. The epoxidation activity compares favorably with those reported for other organotin molybdate, tungstate and vanadate coordination polymers, and is superior to that displayed by the starting materials used for its synthesis (Et3SnBr and NH4VO3) and the metavanadate NBu4VO3.

Titanium-silica catalyst derived from defined metallic titanium cluster precursor: Synthesis and catalytic properties in selective oxidations

A class of titanium-grafted mesoporous silica catalysts has been designed and prepared starting from molecularly defined metal clusters. The organosol mixture of zerovalent Ti13 clusters was impregnated onto the surface of ordered mesoporous silica molecular sieves (MCM-41 and MMM-2) and, after high-temperature calcination, an evenly dispersed non-single-site Ti(IV)nOx-like silica-supported catalyst was obtained. The catalytic solids, fully characterized by microscopic, spectroscopic and porosimetric techniques, showed standard performance in the liquid-phase epoxidation of a cyclic alkene, as limonene, but remarkably high selectivity values in the oxidative carboxylation of styrene, with tert-butylhydroperoxide and carbon dioxide in the presence of tetrabutylammonium bromide as a cocatalyst. Unprecedented high yields, up to 67%, in styrene carbonate were achieved after 24 h, under solvent-free conditions. The catalysts displayed also a noteworthy stability of the performance to repeated recovery and reuse cycles.

Convenient and mild epoxidation of alkenes using heterogeneous cobalt oxide catalysts

A general epoxidation of aromatic and aliphatic olefins has been developed under mild conditions using heterogeneous CoxOy-N/C (x=1,3; y=1,4) catalysts and tert-butyl hydroperoxide as the terminal oxidant. Various stilbenes and aliph

Oxidation of alkenes and sulfides catalyzed by a new binuclear molybdenum bis-oxazoline complex

A novel bis(oxazoline) ligand derived from 1,3-dicyanobenzene was prepared and applied as a ligand for the preparation of a new binuclear molybdenyl complex. This ligand was characterized by UV-Vis, mass, 1H NMR, and FT-IR spectroscopic methods, thermal and elemental analysis and X-ray diffraction. The molybdenum complex was prepared by the reaction of this ligand with MoO2(acac)2. The catalyst was also characterized by FT-IR, UV-Vis, and ICP spectroscopy, elemental and thermal analysis. This catalytic system was efficiently used for the oxidation of alkenes and sulfides in the presence of TBHP. The effect of different solvents and kind of oxygen donor was also studied in the oxidation reactions.

Niobium metallocenes deposited onto mesoporous silica via dry impregnation as catalysts for selective epoxidation of alkenes

A series of niobium catalysts for the selective epoxidation was synthesised by post-synthesis modification of a commercial silica, starting from niobocene dichloride through solventless organometallic precursor dry impregnation (OM-DI) or conventional liquid-phase grafting technique. OM-DI showed to be cheaper, more versatile, less time-consuming and avoided the use of environmentally unfriendly chlorinated solvents. Nb-SiO2 catalysts displayed an excellent performance in the epoxidation of limonene, using aqueous hydrogen peroxide as oxidant. Niobium-silica catalysts were obtained via OM-DI for the first time in this occasion. They showed conversions up to 78% and chemoselectivity to epoxide of 98%. An unexpected regioselectivity to exocyclic epoxide was also observed.