Cobalt-catalyzed partial oxidation of olefins and ethers using molecular oxygen

Co(acac)₃ catalyzes the aerobic oxidation of vinyl aromatic compounds ArCH=CH₂ with formation of ArCO₂H and ArCHO, and also the aerobic oxidation of cyclic ethers with formation of the corresponding lactones.     

One-pot conversion of activated alcohols into 1,1-dibromoalkenes and terminal alkynes using tandem oxidation processes with manganese dioxide

Approaches to the preparation of C₁-homologated dibromoalkenes and terminal alkynes from activated alcohols using one-pot tandem oxidation processes (TOPs) with manganese dioxide are outlined. The conversion of alcohols into dibromoalkenes is described using dibromomethyltriphenylphosphonium bromide and the formation of terminal alkynes was achieved via a sequential one-pot, two-step process utilising the Bestmann-Ohira reagent.     

One-pot conversion of activated alcohols into terminal alkynes using manganese dioxide in combination with the Bestmann-Ohira reagent

The direct conversion of activated primary alcohols into terminal alkynes through a sequential one-pot, two-step process involving oxidation with manganese dioxide and then treatment with the Bestmann-Ohira reagent is described. This transformation proceeds efficiently (59-99% yield) under mild reaction conditions with a range of benzylic, heterocyclic and propargylic alcohols. A tandem variant is also described, which is successful only with highly activated substrates.     

The green and effective oxidation of alcohols to carboxylic acids with molecular oxygen via biocatalytic reaction

A clean and effective alcohol oxidizing system using three enzymes has been developed. Regeneration of NAD⁺ by NADH oxidase with molecular oxygen enabled to oxidize alcohols to carboxylic acids in good yield under mild conditions (25 °C, 1 atm).     

Facile oxidative conversion of alcohols to esters using molecular iodine

A simple, efficient, and high-yield procedure for the oxidative conversion of alcohols to various types of esters and ketones, with molecular iodine and potassium carbonate was successfully carried out.     

Oxidation using activated carbon and molecular oxygen system

This paper describes the utility of an activated carbon–molecular oxygen system, not only in the oxidation of benzylic and allylic alcohols, but also in the direct carbonylation at the benzylic position. The preparation of a variety of heteroaromatic and aromatic compounds, including substituted pyridines, pyrazoles, benzoxazoles, benzimidazoles, benzothiazoles, 2‐substituted imidazoles, indoles, pyrimidin‐2(1H)‐ones, and anthracenes, by oxidative aromatization using the activated carbon–molecular oxygen system is also discussed. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 252–267; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20152     

A new and efficient conversion of olefins into thiiranes using diethoxyoxophosphoranesulfenyl chloride

An expedient synthesis of thiiranes is described that involves electrophilic addition of diethoxyoxophosphoranesulfenyl chloride to alkenes followed by fluoride anion promoted conversion of the intermediate adducts into thiiranes. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 429–433, 1997     

New data on the free radical reaction of alcohols with olefins

Conclusions The radical reaction of alcohols with alkenes-1 proceeds at both carbon atoms of the double bond. As a result, a mixture of the two 1 1 adducts, consisting chiefly of the addition products of the alcohol at the CH₂ group, with a small content (4–13%) of the addition product at the CH group, is formed.     

On the concerted mechanism of the ene reaction of singlet molecular oxygen with olefins. An ab-initio mo study

Ab-initio MO (4-31G) calculations were performed for the reaction of propene with singlet molecular oxygen. The theoretical resultindicates that the concerted mechanism involves a model A-type transition state.     

分子氧选择性氧化醇类的研究进展

综述了分子氧化剂的醇类液相催化氧化的新进展。分别介绍了均相催化、水/有机两相催化、氟两相催化和液固多相催化体系。重点讨论了精细有机合成中有广泛应用前景的绿色氧化方法。预测了均相催化剂的多相化是今后工业化发展的趋势。     

Superoxometal-catalyzed co-oxidation of alcohols and nitrous acid with molecular oxygen

A superoxochromium(III) ion, Cr_aqOO²⁺, acts as a catalyst for the co-oxidation of alcohols and nitrous acid with molecular oxygen according to the stoichiometry: CH₃OH+HNO₂+O₂→CH₂O + NO₃⁻ + H₂O+H⁺. The kinetics are second order in [HNO₂] and independent of the concentrations of the superoxochromium catalyst, substrate, and O₂. The proposed mechanism features the disproportionation of HNO₂ to NO and NO₂, both of which react rapidly with Cr_aqOO²⁺. The Cr_aqOO²⁺/NO reaction generates another equivalent of NO₂ and a mole of Cr_aqO²⁺, the active oxidant. The two-electron oxidation of the alcohol by Cr_aqO²⁺ produces Cr_aq²⁺, which reacts rapidly with O₂ to regenerate the catalyst, Cr_aqOO²⁺. The NO₂/Cr_aqOO²⁺ reaction yields the peroxynitrato complex, Cr_aqOONO₂²⁺, in a dead-end equilibrium process that has no effect on the catalytic reaction. The disproportionation of NO₂ yields the final nitrogen-containing product, NO₃⁻, and regenerates an equivalent of HNO₂. Under a fixed set of conditions, the relative catalytic efficiency (CE) of Cr_aqOO²⁺ decreases as its concentration increases owing to the competition between O₂ and Cr_aqOO²⁺ for the intermediate Cr_aq²⁺.     

The unusual reaction of semiquinone radicals with molecular oxygen

Hydroquinones (benzene-1,4-diols) are naturally occurring chain-breaking antioxidants, whose reactions with peroxyl radicals yield 1,4-semiquinone radicals. Unlike the 1,2-semiquinone radicals derived from catechols (benzene-1,2-diols), the 1,4-semiquinone radicals do not always trap another peroxyl radical, and instead the stoichiometric factor of hydroquinones varies widely between 0 and 2 as a function of ring-substitution and reaction conditions. This variable antioxidant behavior has been attributed to the competing reaction of the 1,4-semiquinone radical with molecular oxygen. Herein we report the results of experiments and theoretical calculations focused on understanding this key reaction. Our experiments, which include detailed kinetic and mechanistic investigations by laser flash photolysis and inhibited autoxidation studies, and our theoretical calculations, which include detailed studies of the reactions of both 1,4-semiquinones and 1,2-semiquinones with O2, provide many important insights. They show that the reaction of O2 with 2,5-di-tert-butyl-1,4-semiquinone radical (used as model compound) has a rate constant of 2.4 +/- 0.9 x 10(5) M-1 s-1 in acetonitrile and as high as 2.0 +/- 0.9 x 10(6) M-1 s-1 in chlorobenzene, i.e., similar to that previously reported in water at pH approximately 7. These results, considered alongside our theoretical calculations, suggest that the reaction occurs by an unusual hydrogen atom abstraction mechanism, taking place in a two-step process consisting first of addition of O2 to the semiquinone radical and second an intramolecular H-atom transfer concerted with elimination of hydroperoxyl to yield the quinone. This reaction appears to be much more facile for 1,4-semiquinones than for their 1,2-isomers.     

Concerning the efficient conversion of epoxy alcohols into epoxy ketones using dioxiranes

Representative epoxy alcohols are cleanly converted into the corresponding epoxy ketones in high yield by selective oxidation using dimethyldioxirane (1a) and its trifluoro analogue (1b) under mild conditions. The oxidation is found to take place leaving the configuration at the epoxy functionality unaffected. The direct oxyfunctionalization of simple cyclic epoxides with the powerful dioxirane 1b provides another attractive method to access epoxy ketones regioselectively.     

Light-mediated transformations of olefins into alcohols: reactions of hydroxyl radicals with cycloalkenes

Reactions of hydroxyl radicals, generated by photodecomposition of hydrogen peroxide in acetonitrile, with a wide variety of cycloalkenes have been examined. The results show that the major reaction is the addition of hydroxyl radicals to the less substituted end of the double bond, furnishing the secondary alcohols. The reactivity pattern and the observed regio- and stereoselectivity clearly reveal that the steric parameters associated with the substrates play a dominant role in directing the addition reactions. More importantly, this study led to the development of a new methodology for the facile conversions of olefins essentially into secondary alcohols, and includes a few examples which demonstrate the potential of the method.     

Organoboranes for synthesis. 5: Stoichiometrically controlled reaction of organoboranes with oxygen under mild conditions to achieve quantitative conversion to alcohols

The reaction of organoboranes with oxygen under mild conditions can be controlled to give an essentially quantitative conversion of all three alkyl groups on boron to the corresponding alcohol. The controlled oxidation is a very clean reaction, with only minor amounts of carbonyl and hydrocarbon products formed. All organoboranes react quite rapidly in the initial stages, but vary considerably in the time required to achieve the desired uptake of oxygen. In contrast to oxidation by alkaline hydrogen peroxide, a portion of this reaction proceeds through alkyl radicals, thus resulting in some loss of stereospecificity. Oxidation of mixed organoboranes reveals that the relative rates of oxidation of alkyl groups on boron are consistent with a radical mechanism, with tertiary ⪢ secondary ⪢ primary in the rate of oxidation. The selective oxidation of one alkyl group in the presence of the other is not possible, due to small differences in relative rates of oxidation. However, thexyl and cyclohexyl groups can be selectively removed from boron in the presence of alkenyl groups. Thus, controlled oxidation of thexyldialkenylborane affords pure dialkenylborinic acid.