Oxidation Of Allylic Alcohols Research Articles

CuCl‐Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1:1 Combination of Phenanthroline and Bipyridine as the Ligands

AbstractWe developed a modified protocol for the oxidation of 2,3‐allenyl alcohols using CuCl with 1:1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested: we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.

Transition metal-free, NaOtBu-O2-mediated one-pot cascade oxidation of allylic alcohols to α,β-unsaturated carboxylic acids

Download options Please wait... Supplementary files Supplementary information PDF (1510K) Article information DOI https://doi.org/10.1039/C2GC36203A Article type Communication Submitted 16 May 2012 Accepted 03 Sep 2012 First published 04 Sep 2012 Download Citation Green Chem., 2012,14, 2996-2998 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Transition metal-free, NaOtBu-O2-mediated one-pot cascade oxidation of allylic alcohols to α,β-unsaturated carboxylic acids S. M. Kim, Y. S. Kim, D. W. Kim and J. W. Yang, Green Chem., 2012, 14, 2996 DOI: 10.1039/C2GC36203A To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Sun Min Kim Young Sug Kim Dong Wan Kim Jung Woon Yang

Selective aerobic oxidation of allylic and benzylic alcohols catalyzed by N-hydroxyindole and copper(I) chloride

In the presence of copper(I) chloride, tert-butyl 1-hydroxy-2-methyl-6-trifluoromethyl-1 H-indole-3-carboxylate acted as a catalyst for the chemoselective aerobic oxidation of allylic and benzylic alcohols. A variety of primary and secondary allylic and benzylic alcohols were oxidized into the corresponding α,β -unsaturated carbonyl compounds in good yields without affecting non-allylic alcohols.

Effective Oxidation of Alcohols under Heterogeneous Conditions with a New Reagent: Manganese Dioxide Supported on Graphite

A new reagent, manganese dioxide supported on graphite, under heterogeneous conditions at reflux is described for the oxidation of benzylic and allylic alcohols into the corresponding aldehydes and ketones, respectively. The main advantage of the present oxidation is that the insoluble solid support, graphite, provides a particular reaction environment capable of enhancing the reaction selectivity and reactivity. Moreover, it turns out to be very profitable in the workup, which becomes reduced to a mere filtration. The mechanism for this oxidation is also discussed.

Theoretical mechanistic study of OH-initiated atmospheric oxidation reaction of allyl alcohol in the presence of O 2 and NO

The potential energy surfaces for the degradation mechanism of OH-initiated allyl alcohol oxidation in the atmosphere have been investigated in detail using QCISD(T)/6-311++G(d,p)//MP2(full)/6-311++G(d,p)+ZPE × 0.95 level of theory for the first time. The theoretical results indicate that the initial OH additions to the double bond will be more feasible than the H abstraction reactions. Two initial formed OH radical adducts IM1 and IM2 will prefer to react with O 2 and NO rather than undergo its self isomerization and dissociation reactions. Our calculational investigations suggest that the major products for the title reaction in the atmosphere are HCHO + CH 2OHCHO, and the minor product is CH 2 CHCHO, which all agree well with the available experimental results.

ChemInform Abstract: Polymer‐Incarcerated Gold—Palladium Nanoclusters with Boron on Carbon: A Mild and Efficient Catalyst for the Sequential Aerobic Oxidation—Michael Addition of 1,3‐Dicarbonyl Compounds to Allylic Alcohols.

We have developed a polymer-incarcerated bimetallic Au−Pd nanocluster and boron as a catalyst for the sequential oxidation−addition reaction of 1,3-dicarbonyl compounds with allylic alcohols. The desired tandem reaction products were obtained in good to excellent yields under mild conditions with broad substrate scope. In the course of our studies, we discovered that the excess reducing agent, sodium borohydride, reacts with the polymer backbone to generate an immobilized tetravalent boron catalyst for the Michael reaction. In addition, we found bimetallic Au−Pd nanoclusters to be particularly effective for the aerobic oxidation of allylic alcohols under base- and water-free conditions. The ability to conduct the reaction under relatively neutral and anhydrous conditions proved to be key in maintaining good catalyst activity during recovery and reuse of the catalyst. Structural characterization (STEM, EDS, SEM, and N2 absorption/desorption isotherm) of the newly prepared PI/CB-Au/Pd/B was performed and co...

ChemInform Abstract: Supported Task‐Specific Ionic Liquid Catalyst for Highly Efficient and Recyclable Aerobic Oxidation of Benzyl Alcohols.

AbstractA novel system is prepared by impregnating ionic liquid immobilized TEMPO and copper salt onto silica. This system successfully catalyzes aerobic oxidation of most benzylic or allylic alcohols in n‐octane to the corresponding aldehydes under O2 atmosphere.

Support-Enhanced Selective Aerobic Alcohol Oxidation over Pd/Mesoporous Silicas

The influence of silica mesostructure upon the Pd-catalyzed selective oxidation of allylic alcohols has been investigated for amorphous and surfactant-templated SBA-15, SBA-16, and KIT-6 silicas. Significant rate enhancements can be achieved via mesopore introduction, most notably through the use of interconnected porous silica frameworks, reflecting both improved mass transport and increased palladium dispersion; catalytic activity decreases in the order Pd/KIT-6 ≈ Pd/SBA-16 > Pd/SBA-15 > Pd/SiO2. Evidence is presented that highly dispersed palladium oxide nanoparticles, not zerovalent palladium, are the catalytically active species. © 2011 American Chemical Society.

Selective liquid-phase oxidation of allyl alcohol to glycidol over MWW type titanosilicalite

The results of the epoxidation of allyl alcohol with 30% hydrogen peroxide over the Ti-MWW catalyst have been presented. The studies were carried out under atmospheric pressure and in the presence of methanol as a solvent. The influence of the following technological parameters on the course of epoxidation was examined: temperature (20–60 °C), the molar ratio of AA/H2O2 (1:1–5:1), methanol concentration (5–90 wt%), catalyst content (0–5.0 wt%), reaction time (5–300 min) and intensity of stirring (0–500 rpm).

Selective catalysis for the oxidation of alcohols to aldehydes in the presence of cucurbit[8]uril

Abstract Efficient selectivity for the supramolecular catalysis by cucurbit[8]uril (Q[8]) for the oxidation of aryl, allyl, and alkyl alcohols to corresponding aldehydes by o-Iodoxybenzoic acid (IBX) in aqueous solvent is reported. The relationship between the catalytic ability of Q[8] and the structure of the substrate has revealed that the catalyst prefers aryl and allyl alcohols to alkyl alcohols, and the conversions of most aryl and allyl alcohols have been increased by 30–50% in the presence of Q[8]. The catalytic selectivity suggests that the IBX oxidation proceeds via a stabilized α-Carbanion intermediate and the supramolecular catalysis should be mechanistically related to the electron density and reactivity of the α-Carbanion.

Mild and Selective Vanadium-Catalyzed Oxidation of Benzylic, Allylic, and Propargylic Alcohols Using Air

Transition metal-catalyzed aerobic alcohol oxidation is an attractive method for the synthesis of carbonyl compounds, but most catalytic systems feature precious metals and require pure oxygen. The vanadium complex (HQ)(2)V(V)(O)(O(i)Pr) (2 mol %, HQ = 8-quinolinate) and NEt(3) (10 mol %) catalyze the oxidation of benzylic, allylic, and propargylic alcohols with air. The catalyst can be easily prepared under air using commercially available reagents and is effective for a wide range of primary and secondary alcohols.

Polymer-Incarcerated Gold−Palladium Nanoclusters with Boron on Carbon: A Mild and Efficient Catalyst for the Sequential Aerobic Oxidation−Michael Addition of 1,3-Dicarbonyl Compounds to Allylic Alcohols

We have developed a polymer-incarcerated bimetallic Au-Pd nanocluster and boron as a catalyst for the sequential oxidation-addition reaction of 1,3-dicarbonyl compounds with allylic alcohols. The desired tandem reaction products were obtained in good to excellent yields under mild conditions with broad substrate scope. In the course of our studies, we discovered that the excess reducing agent, sodium borohydride, reacts with the polymer backbone to generate an immobilized tetravalent boron catalyst for the Michael reaction. In addition, we found bimetallic Au-Pd nanoclusters to be particularly effective for the aerobic oxidation of allylic alcohols under base- and water-free conditions. The ability to conduct the reaction under relatively neutral and anhydrous conditions proved to be key in maintaining good catalyst activity during recovery and reuse of the catalyst. Structural characterization (STEM, EDS, SEM, and N(2) absorption/desorption isotherm) of the newly prepared PI/CB-Au/Pd/B was performed and compared to PI/CB-Au/Pd. We found that while boron was important for the Michael addition reaction, it was found to alter the structural profile of the polymer-carbon black composite material to negatively affect the allylic oxidation reaction.

Ruthenium(II) carbonyl complexes with N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives and triphenylphosphine as effective catalysts for oxidation of alcohols

Ruthenium(II) complexes, [RuCl(L)(CO)(PPh3)2] {where L = N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives}, are prepared from reaction between [RuHCl(CO)(PPh3)3] and N-[di(alkyl/aryl)carbamothioyl]benzamide derivatives in toluene and characterized by elemental analysis and spectral data (electronic, infrared, 1H NMR, and 31P NMR). The combination of [RuCl(L)(CO)(PPh3)2] (0.01 mmol) and N-methylmorpholine-N-oxide (NMO) (3 mmol) is an active catalyst for the oxidation of primary, secondary, cyclic, allylic, aliphatic, and benzylic alcohols to their corresponding aldehydes and ketones at room temperature. The oxidation protocol is simple to operate and gives the corresponding carbonyl compounds good to excellent yields.

Synthetic methods Part (II): oxidation and reduction methods

This Report highlights advances in some of the most commonly used oxidation and reduction reactions, focusing on the literature from 2010. The review is subdivided in a similar fashion to the authors' previous reviews in this area (S. E. Lewis, Annu. Rep. Prog. Chem., Sect. B: Org. Chem., 2010, ; S. E. Lewis, Annu. Rep. Prog. Chem., Sect. B: Org. Chem., 2009, ). Several standout advances have been reported. In the field of oxidation, Yamamoto has reported methods for the reliable enantioselective epoxidation of homoallylic and bishomoallylic alcohols (H. Yamamoto, J. Am. Chem. Soc., 2010, ) an area hitherto underdeveloped in comparison with allylic alcohol oxidation. Tomkinson has developed a dihydroxylation of alkenes which employs a readily prepared, stable malonyl peroxide as oxidant, the significance of which is highlighted by the lack of other metal-free methods to effect the corresponding transformation (N. C. O. Tomkinson et al., J. Am. Chem. Soc., 2010, ). In the field of reduction, Tsuji has reported a catalytic system that is particularly effective for the reduction of highly hindered ketones and even exhibits selectivity for more hindered ketones over less hindered ones (Y. Tsuji et al., Angew. Chem., Int. Ed., 2010, ). Also in the area of ketone reduction, Matsuo has demonstrated reduction of ketones by 1,3-diols in an unusual metal-free process catalysed by a sulfonic acid; high levels of stereoinduction are achieved when a homochiral diol is employed as reductant (J.-I. Matsuo et al., Tetrahedron, 2011, ; J.-I. Matsuo et al., Org. Lett., 2010, ).

Enhanced performance of the catalytic conversion of allyl alcohol to 3-hydroxypropionic acid using bimetallic gold catalysts

One of the strategic building blocks in organic synthesis is 3-hydroxypropionic acid, which is particularly important for the manufacture of high performance polymers. However, to date, despite many attempts using both biological and chemical routes, no large scale effective process for manufacturing 3-hydroxypropionic acid has been developed. One potentially useful starting point is from allyl alcohol, as this can be obtained in principle from the dehydration of glycerol, thereby presenting a bio-renewable green pathway to this important building block. The catalytic transformation of allyl alcohol to 3-hydroxypropionic acid presents interesting challenges in catalyst design, particularly with respect to the control of selectivity among the products that can be expected, as acrylic acid, acrolein and glyceric acid can also be formed. In this paper, we present a novel eco-sustainable catalytic pathway leading to 3-hydroxypropionic acid, which highlights the outstanding potential of gold-based and bimetallic catalysts in the aerobic oxidation of allyl alcohol.

In-situ X-ray Studies of Clean Catalytic Technologies

ABSTRACTThe rational design of new heterogeneous catalysts for clean chemical technologies can be accelerated by molecular level insight into surface chemical processes. In-situ methodologies, able to provide time-resolved and/or pressure dependent information on the evolution of reacting adsorbed layers over catalytically relevant surfaces, are therefore of especial interest. Here we discuss the application of in-situ XPS and in-situ, synchronous DRIFTS/MS/XAS methodologies to elucidate the active site in Pd-catalyzed, selective aerobic oxidation of allylic alcohols.

SBA-15-functionalized TEMPO confined ionic liquid: an efficient catalyst system for transition-metal-free aerobic oxidation of alcohols with improved selectivity

A novel SBA-15-functionalized TEMPO confined ionic liquid [BMIm]Br was found to be a highly efficient and recyclable catalyst system for the transition-metal-free aerobic oxidation of a wide range of structurally diverse alcohols. Thanks to the strong physical confinement of the ionic liquid inside the mesochannels of SBA-15-supported TEMPO, the resulting solid catalyst showed improved selectivity in the aerobic oxidation of allylic alcohols. The catalyst can be recovered and re-used for at least 11 reaction runs without significant loss of either activity or confined IL.

Readily Accessible Oxazolidine Nitroxyl Radicals: Bifunctional Cocatalysts for Simplified Copper Based Aerobic Oxidation

AbstractUsing a two‐step procedure a range of bifunctional oxazolidine nitroxyl radicals have been prepared. The application of these co‐catalysts to the copper‐based aerobic oxidation of alcohols was then investigated. From these studies it was found that the parent tetramethyloxazolidine nitroxyl radical L1 was competent for oxidation in the presence of 2,2′‐bipyridine, and the bifunctional pyridyl‐containing nitroxyl radicals L2 and L3 could be used in the absence of additional coordinating ligands. Following optimization, the scope of this simplified transformation was explored, demonstrating that a range of primary and secondary benzylic alcohols are readily oxidized. In addition, the oxidation of allylic alcohols and hydroquinone can be achieved.

Copper on boehmite: A simple, selective, efficient and reusable heterogeneous catalyst for oxidation of alcohols with periodic acid in water at room temperature

Oxidation of various aliphatic, aromatic, alicyclic, benzylic and allylic alcohols to corresponding carbonyl compounds is studied in water at room temperature over copper on boehmite [Cu/AlO(OH)] catalyst which is prepared from CuCl2·2H2O, pluronic P123 and Al(O-sec-Bu)3. The prepared catalyst was characterized by HR-TEM, SEM-EDX and IR spectroscopy. The reaction conditions for catalytic oxidation of alcohols are optimized with different mole ratio, solvents, and oxidants using 1-phenylethanol system as a model. The scope of the reaction is extended to various types of alcohols. Chemoselectivity, heterogeneity and reusability tests were performed. The use of water as a solvent at room temperature makes the reaction interesting from both an economic and environmental point of view.

Catalytic Activity and Regeneration Property of a Pd Nanoparticle Encapsulated in a Hollow Porous Carbon Sphere for Aerobic Alcohol Oxidation

A core-shell composite consisting of a palladium (Pd) nanoparticle and a hollow carbon shell (Pd@hmC) was employed as a catalyst for aerobic oxidation of various alcohols. The core-shell structure was synthesized by consecutive coatings of Pd nanoparticles with siliceous and carbon layers followed by removal of the intermediate siliceous layer. Structural characterizations using TEM and N(2) adsorption-desorption measurements revealed that Pd@hmC thus-obtained was composed of a Pd nanoparticle core of 3-6 nm in diameter and a hollow carbon shell with well-developed mesopore (ca. 2.5 nm in diameter) and micropore (ca. 0.4-0.8 nm in diameter) systems. When compared to some Pd-supported carbons, Pd@hmC showed a high level of catalytic activity for oxidation of benzyl alcohol into benzaldehyde using atmospheric pressure of O(2) as an oxidant. The Pd@hmC composite also exhibited a high level of catalytic activity for aerobic oxidations of other primary benzylic and allylic alcohols into corresponding aldehydes. The presence of a well-developed pore system in the lateral carbon shell enabled efficient diffusion of both substrates and products to reach the central Pd nanoparticles, leading to such high catalytic activities. This core-shell structure also provided high thermal stability of Pd nanoparticles toward coalescence and/or aggregation due to the physical isolation of each Pd nanoparticle from neighboring particles by the carbon shell: this specific property of Pd@hmC resulted in possible regeneration of catalytic activity for these aerobic oxidations by a high-temperature heat treatment of the sample recovered after catalytic reactions.