Oxidation of alcohols by TBHP in the presence of sub-stoichiometric amounts of MnO2

Commercially available activated MnO₂ has been investigated as a catalyst for the oxidation of alcohols (phenylethanol, 4-methyl- and 4-methoxybenzyl alcohol, trans-cinnamyl alcohol, cyclohexanol, menthol, perillyl alcohol and myrtenol) by TBHP/decane or TBHP/water in MeCN. The activity is highest for benzylic and allylic alcohols. Secondary alcohols yield ketones with good selectivities, while the aldehydes generated from primary alcohols are further oxidized. The process competes with the TBHP catalyzed decomposition. It thus requires the use of excess TBHP and high catalyst loadings to achieve high conversions. However, the low cost of the reagents makes this new protocol convenient for the oxidation of reactive secondary alcohols. The study also suggests that MnO₂ should be proscribed as a reagent to quench excess TBHP in oxidative processes when the synthetic target contains easily oxidizable alcohol functions and when carrying our detailed kinetic monitoring of oxidation processes.     

Effective catalytic oxidation of alcohols and alkenes with monomeric versus dimeric manganese(II) catalysts and t‐BuOOH

Two new Mn(II) complexes, [Mn(C₆H₅COO)(H₂O)(phen)₂](ClO₄)(CH₃OH) ( 1 ) and [Mn₂(μ‐C₆H₅COO)₂(bipy)₄]?2(ClO₄) ( 2 ) (phen = 1,10‐phenanthroline; bipy = 2,2′‐bipyridine), were synthesized and characterized using UV–visible and infrared spectroscopies and single‐crystal X‐ray diffraction analyses. Complexes 1 and 2 have six‐coordinate octahedral geometry around the Mn(II) centre. Complex 1 is a monomer and consists of a deprotonated monodentate benzoate ligand together with two neutral bidentate amine ligands (phen) and a water molecule. Complex 2 has a dinuclear structure in which two Mn(II) ions share two carboxylate groups, adopting a two‐atom bridging mode, and two chelated bipy ligands. Both complexes catalyse the oxidation of alcohols and alkenes in a homogeneous catalytic system consisting of the Mn(II) complex and tert‐butyl hydroperoxide (TBHP) in acetonitrile. The system yields good to quantitative conversions of various alkenes and alcohols, such as styrene, ethylbenzene and cyclohexene to their corresponding ketones, and primary alcohols and 1‐octanol, 1‐heptanol, cyclohexanol, benzyl alcohols and cinnamyl alcohol to their corresponding aldehydes and carboxylic acids. Complexes 1 and 2 exhibit very high activity in the oxidation of cyclohexene to cyclohexanone (ca 80% selectivity) as the main product (ca 94% conversion in 1 h) and of cinnamyl alcohol to cinnamaldehyde (ca 64% selectivity) as the main product (ca 100% conversion in 0.5 h) with TBHP at 70°C in acetonitrile. In addition, optimum reaction conditions were also determined for benzyl alcohol with complexes 1 and 2 and TBHP. Copyright © 2016 John Wiley & Sons, Ltd.     

Dynamical Regime of the Phloroglucinol‐Based Chemical Oscillator in the Presence of Alcohols: Rebirth of Oscillations after an Inhibition Time

This study pertains to the dynamic evolution of the Belousov–Zhabotinsky (BZ) chemical oscillator upon the addition of different aliphatic alcohols (methanol, ethanol, n‐propanol, iso‐propanol, n‐butanol, sec‐butanol, iso‐butanol, and tert‐butanol) at 30°C in a stirred batch reactor. The oscillations are monitored potentiometrically. The experimental findings reveal that the course of the BZ reaction is significantly altered depending on the concentration of the alcohol and the type of the carbon chain present. The mechanism of the alcohol perturbation has been interpreted on account of the experimental results. Besides the qualitative study, a new approach for monitoring the analytical concentration of these alcohols using the BZ oscillatory regime has been explored and it has been found that the alcohol perturbation is directly related to the concentration of the alcohol added, which in turn depends on the inhibition time for the rebirth of oscillatory regime.     

Alcohol Oxidations Using Reduced Polyoxovanadates

A full account of our recently communicated room temperature alcohol oxidation using reduced polyoxovanadates (r‐POV s) is presented. Extensive optimizations revealed optimal conditions employing 0.02 equiv. of r‐POV catalyst Cs₅(V₁₄As₈O₄₂Cl), 5 equiv. tert‐butyl hydrogen peroxide (^t BuOOH ) as the terminal co‐oxidant, in an acetone solvent for the quantitative oxidation of aryl‐substituted secondary alcohols to their ketone products. The substrate scope tolerates most aryl substituted secondary alcohols in good to quantitative yields while alkyl secondary and primary activated alcohols were sluggish in comparison under similar conditions. Catalyst recyclability was successful on a 1.0 mmol scale of starting alcohol 1‐phenylethanol. The oxidation was also successfully promoted by the V^IV /V^V mixed valent polyoxovanadate (POV ) Cs₁₁Na₃Cl₅(V₁₅O₃₆Cl). Finally, a third POV , Cs_2.64(V₅O₉)(AsO₄)₂, was investigated for catalytic activity using our established reaction protocol, but proved ineffective as compared to the other two r‐POV catalysts. This study expands the field of POM ‐mediated alcohol oxidations to include underexplored r‐POV catalysts. While our catalysts do not supplant the best catalysts known for the transformation, their study may inform the development of other novel oxidative transformations mediated by r‐POV s.     

High Performance Pd,PdNi, PdSn and PdSnNi Nanocatalysts Supported on Carbon Nanotubes for Electrooxidation of C2C4 Alcohols

Nanocatalysts Pd, Pd₈Ni₂, Pd₈Sn₂ and Pd₈Sn₁Ni₁ supported on multi‐walled carbon nanotubes (MWCNTs) were successively synthesized by the chemical reduction method in the glycol‐water mixture solvent. Transmission electron microscopy results show that the prepared Pd, Pd₈Ni₂, Pd₈Sn₂ and Pd₈Sn₁Ni₁ nanoparticles are uniformly dispersed on the surface of MWCNTs. The average particle sizes of the nanocatalysts are 3.5–3.8 nm. Electroactivity of the prepared catalysts towards oxidation of ethanol, 1‐propanol, 2‐propanol, n‐butanol, iso‐butanol and sec‐butanol (C2? C4 alcohols) in alkaline medium was studied by cyclic voltammetry and chronoamperometry. The current density obtained for the electrooxidation of C2? C4 alcohols depends on the catalysts and the various structures of the alcohols. Addition of Sn or/and Ni to Pd nanoparticles enhances the electroactivity of the Pd/MWCNT catalyst. Furthermore, the ternary Pd₈Sn₁Ni₁/MWCNT catalyst presents the highest electroactivity for the oxidation of C2? C4 alcohols among the prepared catalysts. Electrocatalytic activity order among propanol isomers and butanol isomers is as follows respectively: 1‐propanol > 2‐propanol, and n‐butanol > iso‐butanol > sec‐butanol > tert‐butanol. This is consistent with the Mulliken charge value of the carbon atom bonded with hydroxyl group in the corresponding alcohol molecule.     

A remarkable effect of ionic liquids in transition-metal-free aerobic oxidation of benzylic alcohols

The transition-metal-free aerobic oxidation of benzylic alcohols is uniquely accelerated by a 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF₆)/PhCF₃ biphasic system and Cs₂CO₃ to afford the corresponding ketones in good yields. The reaction system is also applicable to an oxidative cross-esterification of primary benzyl alcohols with a higher aliphatic alcohol.     

Selective hydrogenation of α,β-unsaturated aldehydes over Pt supported on cerium–zirconium mixed oxide of different composition

Cerium–zirconium mixed oxides with different Ce/Zr ratio were prepared and used as supports for Pt-containing catalysts. The study of the catalysts in the cinnamaldehyde hydrogenation reaction has shown that cinnamaldehyde conversion and cinnamyl alcohol selectivity strongly depend on the CeO₂ content in the support. The highest cinnamyl alcohol yield of 81% was obtained in 105 min at room temperature and atmospheric pressure over the 1%Pt/CeO₂–ZrO₂ catalyst with Ce : Zr atomic ratio equal to 4 : 1.     

Esterification activity and stability of Candida rugosa lipase immobilized into chitosan

Microbial lipase from Candida rugosa immobilized into porous chitosan beads was tested for esterification selectivity with butanol and different organic acids (C2–C12), and butyric acid and different aliphatic alcohols (C2–C10). After 24 h, the acids tested achieved conversions of about 40–45%. Acetic acid was the only exception, and in this case butanol was not consumed. Different alcohols led to butyric acid conversions >40%, except for ethanol, in which case butyric acid was converted only 26%. The system’s butanol and butyric acid were selected for a detailed study by employing an experimental design. The influence of temperature, initial catalyst concentration, and acid:alcohol molar ratio on the formation of butyl butyrate was simultaneously investigated, employing a 2³ full factorial design. The range studied was 37–50°C for temperature (X₁), 1.25–2.5% (w/v) for the catalyst concentration (X₂), and 1 and 2 for the acid:alcohol molar ratio (X₃). Catalyst concentration (X₂) was found to be the most significant factor and its influence was positive. Maximum ester yield (83%) could be obtained when working at the lowest level for temperature (37°C), highest level for lipase concentration (2.5% [w/v]), and center level of acid:alcohol molar ratio (1.5). The immobilized lipase was also used repeatedly in batch esterification reactions of butanol with butyric acid, revealing a half-life of 86 h.     

[IrCl(cod)]2-catalyzed direct oxidative esterification of aldehydes with alcohols

[IrCl(cod)]₂ catalyzed the oxidative esterification of a variety of aldehydes with methanol as a solvent in combination with K₂CO₃ under mild conditions (rt, 12 h). The oxidative esterification reaction of aliphatic aldehydes also took place with olefinic alcohols as reagents in toluene under similar conditions.     

Synthesis of 2‐Phenylquinoline and its Derivatives by Multicomponent Reaction of Aniline,Benzylamine, Alcohols,and CCl4 Catalyzed by FeCl3·6H2O

2‐Phenylquinolines, 2‐phenyl‐3‐methyl‐quinolines, and 2‐phenyl‐3‐ethylquinolines were synthesized in high yields (78–90%) by the reaction of aniline, benzylamine, aliphatic alcohols (ethanol, n‐propanol, n‐butanol), and CCl₄ catalyzed by FeCl₃·6H₂O in tetrachloromethane.     

Hydrogenation of cinnamaldehyde over platinum catalysts: influence of addition of metal chlorides

The effect of addition of metal chlorides to platinum-supported catalysts has been studied in the hydrogenation of cinnamaldehyde in the liquid phase. FeCl₃, SnCl₄ and GeCl₄ were found to be the most effective promoters for the selective synthesis of cinnamyl alcohol. The rate of reaction increased by addition of small amounts of metal chlorides and then decreased at higher contents. Selectivity to cinnamyl alcohol was slightly dependent on the concentration of the additives and on the level of conversion.A reaction mechanism for the hydrogenation of cinnamaldehyde over promoted platinum is suggested.     

Copper(II) Schiff Base Complex Immobilized on Superparamagnetic Fe3O4@SiO2 as a Magnetically Separable Nanocatalyst for Oxidation of Alkenes and Alcohols

A new heterogeneous catalyst containing a copper(II) Schiff base complex covalently immobilized on the surface of silica‐coated Fe₃O₄ nanoparticles (Fe₃O₄@SiO₂‐Schiff base‐Cu(II)) was synthesized. Characterization of this catalyst was performed using various techniques. The catalytic potential of the catalyst was investigated for the oxidation of various alkenes (styrene, α‐methylstyrene, cyclooctene, cyclohexene and norbornene) and alcohols (benzyl alcohol, 3‐methoxybenzyl alcohol, 3‐chlorobenzyl alcohol, benzhydrol and n ‐butanol) using tert ‐butyl hydroperoxide as oxidant. The catalytic investigations revealed that Fe₃O₄@SiO₂‐Schiff base‐Cu(II) was especially efficient for the oxidation of norbornene and benzyl alcohol. The results showed that norbornene epoxide and benzoic acid were obtained with 100 and 87% selectivity, respectively. Moreover, simple magnetic recovery from the reaction mixture and reuse for several times with no significant loss in catalytic activity were other advantages of this catalyst     

Polystyrene‐Supported (Catecholato)oxorhenium Complexes: Catalysts for Alcohol Oxidation with DMSO and for Deoxygenation of Epoxides to Alkenes with Triphenylphosphine

Polymer‐supported catalysts offer practical advantages for organic synthesis, such as improved product isolation, ease of catalyst recycling, and compatibility with parallel solution‐phase techniques. We have developed the (carboxypolystyrene‐catecholato)rhenium catalyst 2 derived from tyramine (=4‐(2‐aminoethyl)phenol), which is effective for alcohol oxidation with dimethylsulfoxide (DMSO) and for epoxide deoxygenation with triphenylphosphine. The supported [Re(catecholato)]catalyst 2 is air‐ and moisture‐stable and can be recovered and used repeatedly without decreasing activity. The procedures work with non‐halogenated solvents (toluene). DMSO for Re‐catalyzed alcohol oxidation is inexpensive and safer for transport and storage than commonly used peroxide reagents. The oxidation procedure was best suited for aliphatic alcohols, and the mild conditions were compatible with unprotected functional groups, such as those of alkenes, phenols, nitro compounds, and ketones (see Tables 1 and 2). Selective oxidation of secondary alcohols in the presence of primary alcohols was possible, and with longer reaction time, primary alcohols were converted to aldehydes without overoxidation. Epoxides (oxirans) were catalytically deoxygenated to alkenes with this catalyst and Ph₃P (see Table 3). Alkyloxiranes were converted to the alkenes with retention of configuration, while partial isomerization was observed in the deoxygenation of cis‐stilbene oxide ( cis‐1,2‐diphenyloxirane). These studies indicate that supported [Re(catecholato)] complexes are effective catalysts for O‐atom‐transfer reactions, and are well suited for applications in organic synthesis.     

Electrochemistry Broadens the Scope of Flavin Photocatalysis: Photoelectrocatalytic Oxidation of Unactivated Alcohols

Riboflavin‐derived photocatalysts have been extensively studied in the context of alcohol oxidation. However, to date, the scope of this catalytic methodology has been limited to benzyl alcohols. In this work, mechanistic understanding of flavin‐catalyzed oxidation reactions, in either the absence or presence of thiourea as a cocatalyst, was obtained. The mechanistic insights enabled development of an electrochemically driven photochemical oxidation of primary and secondary aliphatic alcohols using a pair of flavin and dialkylthiourea catalysts. Electrochemistry makes it possible to avoid using O₂ and an oxidant and generating H₂O₂ as a byproduct, both of which oxidatively degrade thiourea under the reaction conditions. This modification unlocks a new mechanistic pathway in which the oxidation of unactivated alcohols is achieved by thiyl radical mediated hydrogen‐atom abstraction.     

Practical Cu(OAc)2/TEMPO-catalyzed selective aerobic alcohol oxidation under ambient conditions in aqueous acetonitrile

We reported a ligand- and additive-free Cu(OAc)₂/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary and secondary benzylic alcohols, primary and secondary 1-heteroaryl alcohols, cinnamyl alcohols, and aliphatic alcohols to the corresponding aldehydes and ketones. This ambient temperature oxidation protocol is of practical features like aqueous acetonitrile as solvent, ambient air as the terminal oxidant, and low catalyst loading, presenting a potential value in terms of both economical and environmental considerations. Based on the experimental observations, a plausible reaction mechanism was proposed.     

Role of Graphitic Nitrogen and π‐Conjugated Functional Groups in Selective Oxidation of Alcohols: A DFT based Mechanistic Elucidation

Selective oxidation of alcohols to aldehydes is challenging reaction due to its accessibility to overoxidation. In this study, we have made an attempt to unravel the mechanistic aspects of selective oxidation of allyl alcohols that contain multiple functional groups catalyzed by N‐doped graphene. The role of graphitic nitrogen and the presence of π‐conjugated functional groups are demonstrated using the state‐of‐the‐art density functional theory calculations. The detailed reaction mechanism for aerobic oxidation of allyl alcohol (AA) and cinnamyl alcohol (CA) are investigated. The formation of activated oxygen species (AOS) over N‐doped graphene (NG) has been adopted from our previous report. The results revealed that ketonic AOS oxidizes allyl alcohols into aldehydes selectively with a relatively lower activation barrier of 20.1 kcal mol^?1. The oxidation of alcohols with the AOS formed at the edge results in high activation barriers owing to its high thermodynamic stability. Similarly, AOS formed at the center leads to the formation of H₂O₂ along with high activation barriers. As a consequence, AOS formed at the center is less active when compared to ketonic AOS. The overoxidation of aldehyde is only possible due to the formation of H₂O₂. However, it is unlikely to happen due to unfavorable ambient conditions. The presence of multiple π‐conjugated functional groups is responsible for the significant reduction in the activation barriers of the second hydrogen transfer step due to the stabilization of intermediate by increasing the acidic nature of the intermediates. On the basis of the results, a generalized reaction mechanism has been proposed. These results would definitely shed light on the effective fabrication of catalysts for oxidation of alcohol and sustainable energy.     

Oxygen bridged Homobinuclear Mn(II) compounds with Anthranilic acid: Theoretical calculations,oxidation and catalase activity

Two new homobinuclear manganese compounds with mixed ligands, [Mn₂(μ_1,1–2‐NH₂C₆H₄COO)₂(phen)₄](ClO₄)2(CH₃OH) ( 1 ), and [Mn₂(μ_1,3–2‐NH₂C₆H₄COO)₂(bipy)₄](ClO₄)2 ( 2 ) (NH₂C₆H₄COOH = anthranilic acid, bipy = 2,2′‐bipyridine, phen = 1,10‐ phenanthroline) were synthesized and thoroughly characterized by elemental analysis, IR, UV and single crystal X‐ray crystallography. X‐ray structure analysis shows that in the mono‐ and bidentate carboxylate bridged compounds, Mn–Mn distances of 1 and 2 are 3,461 Å, and 4,639 Å, respectively. The energy of the compounds was determined with a DFT (Density Functional Theory) calculation on B3LYP/6‐31G(d,p) optimized geometry by using the B3LYP/6‐31G(d,p) basis set. These compounds acts as biomimetic catalyst and show catalase‐like activity for the hydrogen peroxide dismutation at room temperature in different solvents with remarkable activity (TOF, Turnover frequency = mol of subst./(mol of cat. × time)) up to 12640 h^?1 with 1 , and 17910 h^?1 with 2 in Tris–HCl buffer). Moreover, the catalytic activity of 1 and 2 has been studied for oxidation of alcohols (cinnamyl alcohol, benzyl alcohol, cyclohexanol, 1‐octanol and 1‐heptanol) and alkenes (cyclohexene, styrene, ethyl benzene, 1‐octene and 1‐hexene) in a homogeneous catalytic system consisting t‐butylhydroperoxide (TBHP) as an oxidant in acetonitrile. Both compounds exhibited very high activity in the oxidation of cyclohexene to cyclohexanone (~80% selectivity, ~99% conversion in 1 h, TOF = 243 h^?1 and 226 h^?1) and cinnamyl alcohol to cinnamaldehyde (~64% selectivity) as the main product with very high TOF value (9180 h^?1 and 13040 h^?1 in the first minute of reaction) (~100% conversion in 0.5 h) with TBHP at 70 °C in acetonitrile, for 1 and 2 , respectively.     

Oxidation of sec‐alcohols with Ru(II)‐bearing microgel star polymer catalysts via hydrogen transfer reaction: Unique microgel‐core catalysis

Oxidation of sec‐alcohols was investigated with ruthenium‐bearing microgel core star polymer catalysts [Ru(II)‐Star]. The star polymer catalysts were directly prepared via RuCl₂(PPh₃)₃‐catalyzed living radical polymerization of methyl methacrylate (MMA), followed by the arm‐linking reaction with ethylene glycol dimethacrylate ( 1 ) in the presence of diphenylphosphinostyrene ( 2 ). The Ru(II)‐Star efficiently and homogeneously catalyzed the oxidation of 1‐phenylethanol ( S1 ) to give a corresponding ketone (acetophenone) in higher yield (92%) than the analogs of polymer‐supported ruthenium complexes. Importantly, the star catalyst afforded high recycling efficiency in the oxidation. They held catalytic activity against three times catalysis even though they were recovered under air‐exposure, whereas the conventional RuCl₂(PPh₃)₃ lost the activity for same recycling procedure due to the deactivation by oxygen. The stability of the star catalysts during the recycle experiment was confirmed by detailed spectroscopic characterization. The star polymers also catalyzed oxidation for a wide range of sec‐alcohols with aromatic and aliphatic groups. The substrate affinity was different from that with RuCl₂(PPh₃)₃, suggesting the unique selectivity caused by the specific structure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

The Regio‐ and Stereospecific Intermolecular Dehydrative Alkoxylation of Allylic Alcohols Catalyzed by a Gold(I) N‐Heterocyclic Carbene Complex

A 1:1 mixture of [AuCl(IPr)] (IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidine) and AgClO₄ catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to form allylic ethers. These transformations are regio‐ and stereospecific with preferential addition of the alcohol nucleophile at the γ‐position of the allylic alcohol syn to the departing hydroxyl group and with predominant formation of the E stereoisomer. The minor α regioisomer is formed predominantly through a secondary reaction manifold involving regioselective γ‐alkoxylation of the initially formed allylic ether rather than by the direct α‐alkoxylation of the allylic alcohol.     

Allylation of Carbonyl Compounds Mediated by Aluminum/Fluoride Salts in Water

A novel mediator (Al/KF) has been developed and employed in the Barbier‐type alkylations of various aldehydes and ketones with alkyl halide in water. The carbonyl compounds could be effectively converted into corresponding homoallylic alcohol in good yields only when allyl bromides or substituted allyl bromides were used as halides. Aromatic aldehydes could afford homoallylic alcohols in high yields, unfortunately, the allylation of aromatic aldehyde substituted by nitro‐ or amino‐group could not proceed smoothly, and the allylation yields of ketones and aliphatic carbonyl compounds were lower under the same condition. The diastereoselectivity and regioseletivity of the reaction have also been studied, the predominant products preferred the erythro‐ or anti‐isomer in dominant γ‐adduct by using Al/KF mediated allylation of benzaldehydes with cinnamyl bromide and ethyl 4‐bromo‐2‐butenoate in water.