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Relevant academic research and scientific papers

Manganese(II)/Picolinic Acid Catalyst System for Epoxidation of Olefins

An in situ generated catalyst system based on Mn(CF3SO3)2, picolinic acid, and peracetic acid converts an extensive scope of olefins to their epoxides at 0 °C in 5 min, with remarkable oxidant efficiency and no evidence of radical behavior. Competition experiments indicate an electrophilic active oxidant, proposed to be a high-valent Mn = O species. Ligand exploration suggests a general ligand sphere motif contributes to effective oxidation. The method is underscored by its simplicity and use of inexpensive reagents to quickly access high value-added products.

Rhodium acetate-catalyzed aerobic Mukaiyama epoxidation of alkenes

Mukaiyama epoxidation of alkenes under oxygen catalyzed by rhodium acetate with isobutyraldehyde as the reducing agent is as or more effective than previously reported procedures. A variety of alkenes, including terpenes and cholesterol derivatives, were oxidized. And high regioselectivity for monoepoxidation was observed with neryl, geranyl, and linalyl acetates.

Non-heme iron catalysis in CC, C-H, and CH2 oxidation reactions. Oxidative transformations on terpenoids catalyzed by Fe(bpmen)(OTf)2

The oxidation of terpene olefins with hydrogen peroxide in the presence of the non-hemo catalyst 5a afforded mixtures of epoxides whose composition was dependent upon the oxidation protocol used in each case. With terpenoid enones, the mixtures obtained evolved from clean epoxidation of α-ionone 23 to the clean allylic oxidation of damascone 28 due to the progressive deactivation of the electron density on the double bonds present in this series. The oxidation of bicyclic and tricyclic terpenoids afforded oxidation products coming from epoxidation, to olefin degradation, methyne and methylene activation products. Probably, the most attractive result was the synthesis of the Magnus lactone 46, from the tricyclic ether 45, with 88% yield and 100% conversion.

An investigation into oxo analogues of molybdenum olefin metathesis complexes as epoxidation catalysts for alkenes

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.

Epoxidation of alkenes with H2O2 generated in situ from alcohols and molecular oxygen using N-hydroxyphthalimide and hexafluoroacetone as catalysts

A new epoxidation method of olefins with hydrogen peroxide and/or α- hydroxy hydroperoxide which are generated in situ from an alcohol and molecular oxygen was developed. A variety of alkenes were smoothly epoxidized with molecular oxygen in the presence of an alcohol under the influence of hexafluoroacetone (HFA) and N-hydroxyphthalimide (NHPI) as catalysts. The reaction involves the formation of α-hydroxy hydroperoxide and/or hydrogen peroxide derived from 1-phenylethanol and dioxygen by the action of NHPI and the active oxygen transfer from these hydroperoxides to HFA, giving 2- hydroperoxyhexafluoro-2-propanol which serves as the actual epoxidizing agent.

Diastereoselective and regioselective epoxidations of allylic alcohols by the in situ-generated dioxirane of 2,2,2-trifluoroacetophenone

The diastereoselective epoxidations of cyclohex-2-en-1-ols and the regioselective epoxidations of geraniol and their acetates using the in situ- generated dioxirane from 2,2,2-trifluoroacetophenone are reported along with comparable epoxidations with Oxone. (C) 2000 Elsevier Science Ltd.

Selective epoxidation of monoterpenes with methyltrioxorhenium and H2O2

In the presence of pyridine as a co-catalyst, CH3ReO3 catalyses the epoxidation of terpenes such as α-pinene with H2O2 with minimal rearrangement of the epoxide. Pyridine is also critical to suppress isomerisation of the olefin substrate (in case of nerol, geraniol). The reaction can be directed towards selective single or double epoxidation, or in one step towards the rearranged product (e.g. from linalool to the ring- closure product linalool oxide.

Selective Oxidation of Monoterpenes with Hydrogen Peroxide Catalyzed by Peroxotungstophosphate (PCWP)

Catalytic epoxidation of monoterpenes with aqueous hydrogen peroxide catalyzed by peroxotungstophosphate (PCWP) under biphase conditions using chloroform as the solvent was examined.A variety of terpenes was oxidized to the corresponding monoepoxides or diepoxides in good yields under mild conditions.For example, limonene (1) was converted into limonene oxide (1a) in which the cyclohexene double bond was selectively epoxidized in almost quantitative yield.The oxidation of γ-terpinene (2) with 2.2 equiv of 35percent H2O2 took place with high stereoselectivity to give cis-diepoxide 2c.In terpenes bearing electron-withdrawing groups such as neryl acetate (3), geranyl acetate (4), citral (5), and geranyl nitrile (6), the double bonds remote from the substituents were epoxidized in preference to the others.The epoxidation of linalool (9) by the present catalyst-oxidant system produced the cyclic products, hydroxy furan 9a and hydroxy pyran 9b, rather than epoxide. tert-Butyl alcohol was successfully employed as the solvent by treating a hydrogen peroxide solution of tert-butyl alcohol with MgSO4 prior to use.The regioselectivities in the epoxidation of monoterpenes can be favorably explained from the electron densities of the double bonds which were estimated using the CAChe system.

THE HIGHLY EFFICIENT OXIDATION OF OLEFINS, ALCOHOLS, SULFIDES AND ALKANES WITH HETEROAROMATIC N-OXIDES CATALYZED BY RUTHENIUM PORPHYRINS

The oxygen atom transfer reactions from 2,6-disubstituted pyridine N-oxides to olefins, allyl or benzyl alcohols and sulfides were efficiently catalyzed by ruthenium porphyrins, and these substrates were converted into epoxides, aldehydes and sulfoxides, respectively, with high selectivity.These oxidations also proceeded using other heteroaromatic N-oxides, such as pyrazine N-oxides, as oxidants.The catalytic activity of ruthenium porphyrin complexes was enhanced by the addition of a small amount of HCl or HBr.In the presence of these acids, the oxidations of alkanes or aliphatic alcohols with 2,6-dichloropyridine N-oxides were also efficiently catalyzed by ruthenium porphyrin complexes, and alcohols or ketones were afforded as oxidation products with high selectivity.In the hydroxylation of adamantane, ruthenium porphyrins work very efficiently as catalysts, giving a turnover number of up to 120000.This system offers practical advantages, such as mild conditions, tractability of oxidants and easy overall procedures.In the case of the reactions with HCl or HBr, one possibility in the reaction mechanism is that the activity of ruthenium porphyrins is enhanced in part by the coordination of Cl- or Br- as axial ligands.