1192-78-5Relevant academic research and scientific papers
OXIDATION OF ALCOHOLS WITH OXOPEROXOBIS-(N-PHENYLBENZOHYDROXAMATO)MOLYBDENUM(VI)
Tomioka, Hiroki,Takai, Kazuhiko,Oshima, Koichiro,Nozaki, Hitosi,Toriumi, Koshiro
, p. 4843 - 4846 (1980)
The title complex oxidizes primary and secondary alcohols to the corresponding carbonyl compounds.Stereoselective epoxidation of allylic alcohols is also described.
Zeolite-Catalyzed Epoxidation Of Allylic Alcohols
Antonioletti, R.,Bonadies, F.,Locati, L.,Scettri, A.
, p. 3205 - 3206 (1992)
4 Angstroem molecular sieves have shown to be efficient catalysts for regio- and stereoselctive epoxidation of allylic alcohols.
Regio-, diastereo-, and chemoselectivities in the dioxirane oxidation of acyclic and cyclic allylic alcohols by methyl(trifluoromethyl)dioxirane (TFD): A comparison with dimethyldioxirane
Adam, Waldemar,Paredes, Rodrigo,Smerz, Alexander K.,Veloza, L. Angela
, p. 349 - 354 (1998)
The solvent-dependent shift in the regioselectivity of the geraniol epoxidation by methyl(trifluoromethyl)dioxirane (TFD) reveals that as for the less reactive dimethyldioxirane (DMD). hydrogen bonding stabilizes the transition state of the epoxidation. In protic media, the hydrogen bonding is exerted intermolecularly by the solvent, whereas in unpolar, non-hydrogen-bonding solvents intramolecular assistance through the adjacent hydroxy functionality comes into the play and the attack on the allylic alcohol moiety is favored. For chiral allylic alcohols, additional steric interactions control the π-facial selectivity in the conformationally fixed transition state. Analogous to DMD, the preferred dihedral angle in the hydrogen-bonded transition state of the TFD epoxidation constitutes approximately 130°, but contrary to DMD and for synthetic purposes important, the allylic alcohols and derivatives 1 and 3-5 investigated here are chemoselectively epoxidized by TFD without formation of the corresponding enones.
Catalytic epoxidation activity of keplerate polyoxomolybdate nanoball toward aqueous suspension of olefins under mild aerobic conditions
Rezaeifard, Abdolreza,Haddad, Reza,Jafarpour, Maasoumeh,Hakimi, Mohammad
, p. 10036 - 10039 (2013)
Catalytic efficiency of a sphere-shaped nanosized polyoxomolybdate {Mo 132} in the aerobic epoxidation of olefins in water at ambient temperature and pressure in the absence of reducing agent is exploited which resulted good-to-high yields and desired selectivity.
Hydroxyselenation of Allylic Alcohols
Cooper, Matthew A.,Ward, A. David
, p. 2327 - 2330 (1995)
Hydroxyselenation of terminal or cyclic allylic alcohols occurs with high regio- and stereoselectivity to give β,β'-dihydroxyphenylselenated adducts in high yields.A mechanism for this selectivity is proposed.The utility of these adducts is illustrated by the conversion of the hydroxyselenide (9a) to the epoxide (11) via the intermediacy of a selenone.
Synthesis and structural characterization of molybdenum(VI) and iron(II) coordination compounds with S-alkyl-N-methyl-S-(2-pyridyl)sulfoximines and catalytic epoxidation activity of the molybdenum complexes
Brussaard, Yvonne,Olbrich, Falk,Schaumann, Ernst
, p. 13160 - 13166 (2013)
Coordination compounds oxido(diperoxido)(S-butyl-N-methyl-S-(2-pyridyl) sulfoximine)molybdenum(VI), [MoO(O2)2{SO(NMe) nBu(NC5H4)}] (5c), and bis{(dichlorido)(N,S- dimethyl-2-pyridylsulfoximine)iron(II)}, tetrahydrofuran solvate (1:1) (6), [FeCl2{SO(NMe)Me(NC5H4)}]2· THF are prepared from the free ligand 4 and molybdenum(VI) oxidediperoxide(dihydrate) and iron dichloride, respectively. The crystal structures reveal a trigonal bipyramid with the pyridine ring and the single oxygen on molybdenum in a trans arrangement for 5c and a planar μ2-Cl2Fe2 ring with trans-oriented exocyclic Cl atoms for 6 whereas the structures of the N,N-dicoordinated ligands are only little effected by the metals. Coordination compounds (5) efficiently catalyze the epoxidation of cyclooctene or of monosubstituted alkenes by tert-butyl hydroperoxide.
A SUPPORTED EPOXIDATION CATALYST FOR NUCLEOPHILIC OLEFINS
Okamoto, Yasushi,Still, W. Clark
, p. 971 - 974 (1988)
A polystyrene-supported peptid-linked epoxidation catalyst is described and its utility for the discovery of new epoxidants is discussed.
Effect of Transition Metal Compounds on the Cyclohexene Oxidation Catalyzed by N-Hydroxyphthalimide
Kuznetsova,Kuznetsova,Yakovina,Zudin,Bal’zhinimaev
, p. 735 - 743 (2018)
Abstract: N-Hydroxyphthalimide (NHPI) is an efficient organic catalyst in the oxidation reactions of organic compounds occurring via a radical mechanism, often used together with redox-active ions or transition metal complexes. In this work the catalytic action of NHPI is studied together with Cu(II), Fe(III), and Mo(VI) compounds in the reaction of aerobic oxidation of cyclohexene in an acetonitrile solution at 60°C. It was found that iron(III) benzoate accelerates the reaction by rapidly generating the active form of the phthalimide-N-oxyl radical (PINO) catalyst, but does not cause decomposition of the hydroperoxide. The oxidation product is 2-cyclohexenyl hydroperoxide formed with a selectivity of 85% at a cyclohexene conversion of 50%. Copper(II) acetate initiates oxidation and is capable of catalyzing the radical decomposition of the hydroperoxide and secondary oxidation of allyl oxygenates. When reaching a cyclohexene conversion close to 80%, the overall selectivity to the main products, 2-cyclohexenyl hydroperoxide and 2-cyclohexen-1-on, was 70%. The addition of iron(III) and molybdenum(VI) compounds led to the intensive generation of hydroperoxide and its activation as an electrophilic reactant capable of cyclohexene epoxidation. As a result of the use of the multifunctional three-component NHPI–Mo(VI)–Fe(III) catalyst, cyclohexene oxidation by molecular oxygen occurred with the formation of epoxycyclohexane. The selectivity to the products of cyclohexene epoxidation was close to 50%, which is a value expected from theory.
An investigation into oxo analogues of molybdenum olefin metathesis complexes as epoxidation catalysts for alkenes
Anderson, James C.,Smith, Neil M.,Robertson, Michelle,Scott, Mark S.
, p. 5344 - 5346 (2009)
The oxo-imido molybdenum complex 2a is an effective catalyst at low catalyst loadings (0.5 mol % or below) for the epoxidation of a range of alkenes with tBuOOH in PhMe at 90 °C. Reactions are complete in less than 4 h and the products are isolated in high yields. The catalytic system is chemoselective for the epoxidation of electron-rich alkenes and allylic alcohols.
The mechanism of oxidation of allylic alcohols to α,β-unsaturated ketones by cytochrome P450 a
Bellucci, Giuseppe,Chiappe, Cinzia,Pucci, Laura,Gervasi, Pier Giovanni
, p. 871 - 874 (1996)
The oxidation of cyclohex-2-en-1-ol, a simple model substrate for allylic alcohols, is catalyzed by several P450 isoenzymes and leads exclusively to cyclohex-2-en-1-one. No double bond epoxidation or C(4) hydroxylation have been observed. The large primary kinetic isotope effect measured using [2H]-1-cyclohex-2-en-1-ol is consistent with an at least partially rate limiting breaking of the C(1)-H bond. The mass spectrometric analysis of cyclohex-2-en-1-one obtained from [18O]cyclohex-2-en-1-ol has established that a gem-diol intermediate is involved, even if a dual hydrogen abstraction pathway may contribute to the reaction.
