Oxidation allyl alcohol

Synonyms AI3-50540 Allyl alcohol oxide BRN 0383562 CCRIS 1052 EINECS 209-128-3 Epihydric alcohol Epihydrin alcohol l,2-Epoxy-3-hydroxypropane 2,3-Epoxypropanol 2,3-Epoxy-1-propanol Epoxypropyl alcohol Glycide Glycidyl alcohol l-Hydroxy-2,3-epoxy-propane Hydroxymethyl ethylene oxide 2-Hydroxymethyloxiran 3-Hydroxypropylene oxide NCI-C55549 NSC-C55549 Oxiranemethanol Oxiranylmethanol UN 2810. 

Considering the excellent chemoselectivity observed in the allylic oxidation of dehydroepiandrosterone (Scheme 16), it was interesting to evaluate the selective allylic alcohol oxidation in the presence of a secondary saturated hydroxyl group using the BiCls/f-BuOOH system. This study was performed using androst-... 

Scheme 18 BiCl3-catalyzed allylic alcohol oxidation of androst-4-ene-3p,17P-diol with t-BuOOH...

Nickel-containing polyfluorometalated [Ni(H20)H2FeNaWi7055] was capable of catalytic activation of hydrogen peroxide for allylic alcohol oxidation in biphasic conditions (catalyst substrate ratio 1 1000). Homoallylic alcohols are significantly less reactive than allylic homologues and cis > trans reactivity is found also in this case. 

Synonyms Allyl alcohol oxide epihydrin alcohol l,2-epoxy-3-hydroxypropane 2,3-epoxy-l-propanol ( )-2,3-epoxy-1-propanol glycide ( )-glycidol (RS)-glycidol dl-glycidol glycidyl alcohol hydroxy-l,2-epoxypropane l-hydroxy-2,3-epoxypropane 2-(hydroxymethyl)oxirane 3-hydroxypropylene oxide oxiranyl-methanol racemic glycidol... 

The large-scale production of esomeprazole is now successfully achieved by asymmetric oxidation of the same sulfide intermediate as is used in the production of omeprazole (Scheme 2.5). Using the titanium-based catalyst originally developed by K. Barry Sharpless for allyl alcohol oxidation [56] and by H.B. Kagan for certain sulfide oxidations [57], a process was developed that could achieve initial enantiomeric excesses of about 94% [53]. During the production process, the optical purity is further enhanced by the preparation of esomeprazole magnesium salt, with subsequent re-crystallization. 

A. Silver-Mediated Selective Benzylic and Allylic Alcohol Oxidation / 17... 

The kinetics of allyl alcohol oxidation on the rhombic phase of the V-MoOs catalyst can be described by the equation... 

This Equation does not differ from the usual Mars-Van Krevelen redox equation. The rate constants of the separate steps of oxidation and reduction from Equation (11) are listed in Table 3. They are-compared in the same Table with the rate constants determined separately from the experiments on reduction and reoxidation. The coincidence between the calculated and experimental rate constants confirms the proposed redox mechanism of allyl alcohol oxidation over the rhombic phase of V-MoOg catalyst. 

A graphic scheme of allyl alcohol oxidation is represented in Eig.7. The ESR study of thi.s reaction in situ has shown that the -active sites... 

Simultaneously with the investigations on Pt, the reactivity of the primary C3 alcohols on gold elecrodes in acid media (0.5 mol dm H2SO4) was studied by the same authors. The results obtained, in agreement with previous observations, confirm once more that no reactions with n-propanol occur at a gold electrode in acid medium. Bulk allyl alcohol oxidation leads to the formation of CO2 and acrolein, while propargyl alcohol electrooxidation produces CO2 and propargyl aldehyde. Some of the main conclusions are as follows ... 

Pyridinium Chlorochromate. The need for improved oxidation of primary alcohols and greater ease for isolation of products prompted further research into the nature of Cr(VI) reagents. Corey found that addition of pyridine to a solution of chromium trioxide in aqueous HCl allowed crystallization of a solid reagent characterized as 31, pyridinium chlorochromate (PCC). This reagent was superior for the conversion of primary alcohols to aldehydes in dichloromethane but less efficient than the Collins oxidation when applied to allylic alcohols. Oxidation of 1-heptanol with PCC in dichloromethane gave 78% of heptanal, for example. As stated by Corey, PCC is an effective oxidant in dichloromethane although aqueous chlorochromate species are not very effective oxidants. Oxidation of secondary alcohols to ketones is straightforward, as in Banwell s synthesis of y-lycorane, in which 32 was oxidized by PCC to the ketone (33). ... 

These results are consistent with the results of allyl alcohol oxidation (Scheme 12). Propene gives acetone as the major product (90%) and propanal as a minor product (—10%). With aUyl alcohol the corresponding products are hydroxy acetone (5) and 2-hydroxypropanal (4) in a ratio of 1 2.7. Thus, the hydroxyl must be directing the palladium to mainly add to the central carbon to give the intermediate corresponding to 6. 

Lee, A., Gee, J. and Theyers, H. (2000). Aspects of Allylic Alcohol Oxidation - A Bimetallic Heterogeneous Selective Oxidation Catalyst, Green Chem., 2, pp. 279-282. 

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