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Rhodium-Catalyzed Regioselective Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes Using Formic Acid
A rhodium-catalyzed hydroformylation of alkynes with formic acid was developed. The method provides α,β-unsaturated aldehydes in high yield and E-selectivity without the need to handle toxic CO gas.
Fan, Chao,Hou, Jing,Chen, Yu-Jia,Ding, Kui-Ling,Zhou, Qi-Lin
supporting information
p. 2074 - 2077
(2021/04/05)

Pt-Catalyzed selective oxidation of alcohols to aldehydes with hydrogen peroxide using continuous flow reactors
The oxidation of alcohols to aldehydes is a powerful reaction pathway for obtaining valuable fine chemicals used in pharmaceuticals and biologically active compounds. Although many oxidants can oxidize alcohols, only a few hydrogen peroxide oxidations can be employed to continuously synthesize aldehydes in high yields using a liquid-liquid two-phase flow reactor, despite the possibility of the application toward a safe and rapid multi-step synthesis. We herein report the continuous flow synthesis of (E)-cinnamaldehyde from (E)-cinnamyl alcohol in 95%-98% yields with 99% selectivity for over 5 days by the selective oxidation of hydrogen peroxide using a catalyst column in which Pt is dispersed in SiO2. The active species for the developed selective oxidation is found to be zero-valent Pt(0) from the X-ray photoelectron spectroscopy measurements of the Pt surface before and after the oxidation. Using Pt black diluted with SiO2as a catalyst to retain the Pt(0) species with the optimal substrate and H2O2introduction rate not only enhances the catalytic activity but also maintains the activity during the flow reaction. Optimizing the contact time of the substrate with Pt and H2O2using a flow reactor is important to proceed with the selective oxidation to prevent the catalytic H2O2decomposition.
Kon, Yoshihiro,Nakashima, Takuya,Yada, Akira,Fujitani, Tadahiro,Onozawa, Shun-Ya,Kobayashi, Shū,Sato, Kazuhiko
supporting information
p. 1115 - 1121
(2021/02/16)

Ligand coordination sphere effect of Schiff base cis-dioxomolybdenum(VI) complexes in selective catalytic oxidation of alcohols
Several cis-dioxomolybdenum(VI) complexes with Schiff bases-derived ligands were synthesized and fully characterized. The catalytic performances of these complexes were tested in the alcohol oxidation under solvent-free condition using H2O2 as oxidant giving high results. The influence of the oxygen, sulfur, and nitrogen atom within the coordination sphere around the molybdenum center was studied (S?>?N?>?O). From this study, we suggest that there exists a relationship between the electronegativity of the atom and the catalytic performance in alcohol oxidation.
Liu, Haiwen,Zhuo, Zihan,Zhang, Yan,Wei, Hang,Zhang, Wenxin,Li, Tong,Mao, Zuodong,Wang, Weili
p. 1253 - 1261
(2021/08/13)

Radical induced disproportionation of alcohols assisted by iodide under acidic conditions
The disproportionation of alcohols without an additional reductant and oxidant to simultaneously form alkanes and aldehydes/ketones represents an atom-economical transformation. However, only limited methodologies have been reported, and they suffer from a narrow substrate scope or harsh reaction conditions. Herein, we report that alcohol disproportionation can proceed with high efficiency catalyzed by iodide under acidic conditions. This method exhibits high functional group tolerance including aryl alcohol derivatives with both electron-withdrawing and electron-donating groups, furan ring alcohol derivatives, allyl alcohol derivatives, and dihydric alcohols. Under the optimized reaction conditions, a 49% yield of 5-methyl furfural and a 49% yield of 2,5-diformylfuran were obtained simultaneously from 5-hydroxymethylfurfural. An initial mechanistic study suggested that the hydrogen transfer during this redox disproportionation occurred through the inter-transformation of HI and I2. Radical intermediates were involved during this reaction.
Huang, Yang,Jiang, Haiwei,Li, Teng,Peng, Yang,Rong, Nianxin,Shi, Hexian,Yang, Weiran
supporting information
p. 8108 - 8115
(2021/10/29)

Iodine-catalyzed alcohol disproportionation method
The invention relates to the technical field of catalysis, in particular to an iodine-catalyzed alcohol disproportionation method which comprises the following steps: sequentially adding alcohol, iodine and a solvent into a high-temperature and high-pressure reaction kettle, introducing a certain amount of nitrogen, conducting reacting for a certain time, collecting an organic phase after the reaction is ended, and conducting fractionating to obtain corresponding alkane and aldehyde/ketone. Alcohol disproportionation is efficient and atom-economical conversion without any additional oxidizing agent and reducing agent, and hydrocarbon and aldehyde/ketone molecules which are easy to separate can be formed at the same time. Meanwhile, the method has wide functional group tolerance, various substrate samples including aryl alcohol derivatives, heterocyclic alcohol derivatives, allyl alcohol derivatives and dihydric alcohol are tested, and the result shows that most of the substrate samples show good or extremely good yield.
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Paragraph 0034-0035

(2021/06/13)

Palladium/Copper-catalyzed Oxidation of Aliphatic Terminal Alkenes to Aldehydes Assisted by p-Benzoquinone
The development of an anti-Markovnikov Wacker-type oxidation for simple aliphatic alkenes is a significant challenge. Herein, a variety of aldehydes can be selectively obtained from various unbiased aliphatic terminal alkenes using PdCl2(MeCN)2/CuCl in the presence of p-benzoquinone (BQ) under mild reaction conditions. Isomerization of the terminal alkene to the internal alkene was suppressed via slow addition of the starting material to the reaction mixture. In addition to the Pd catalyst, CuCl and BQ were essential in order to obtain the anti-Markovnikov product with high selectivity. Terminal alkenes bearing a halogen substituent afforded their corresponding aldehydes with high anti-Markovnikov selectivity. The halogen acts as a directing group in the reaction. DFT calculations indicate that a μ-chloro Pd(II)?Cu(I) bimetallic species with BQ coordinated to Cu is the catalytically active species in the case of a terminal alkene without a directing group.
Komori, Saki,Yamaguchi, Yoshiko,Murakami, Yuka,Kataoka, Yasutaka,Ura, Yasuyuki
p. 3946 - 3955
(2020/07/06)

Highly γ-Regioselective 1,2-Addition of α,β-Unsaturated Oxime Ethers with Allylzinc Bromides: A Straightforward Approach for the Synthesis of Homoallylic Amines
A highly regioselective reaction between allylzinc bromide reagents and α,β-unsaturated oxime ethers for the one-step synthesis of the homoallylic amines is reported. This process is a regioselective 1,2-addition reaction providing a new γ-position with carbon-carbon bond formation. Furthermore, the reaction substrates are widely applicable and can be produced in a high yield.
Yang, Bo,Zhang, Songlin
supporting information
p. 3736 - 3746
(2019/09/30)

Selective Aerobic Oxidation of Alcohols with NO3? Activated Nitroxyl Radical/Manganese Catalyst System
A homogeneous Mn(NO3)2/2,2,6,6-tetramethylpiperidin-1-yl)oxyl/2-picolinic acid catalyst system is highly active and versatile for the selective aerobic oxidation of alcohols (2,2,6,6-tetramethylpiperidin-1-yl)oxyl=TEMPO, 2-picolinic acid=PyCOOH). The catalytic method enables near quantitative conversion of various primary alcohols to the respective aldehydes using a very simple reaction setup and workup. This study presents findings on the catalyst stability and mechanisms of deactivation. The results show that NO3? plays a crucial catalytic role in the reaction as a source of oxygen activating NOx species. Yet, disproportionation of NO3? to the volatile NO2 during the reaction leads to catalyst deactivation under open air conditions. Catalyst deactivation through this route can be overcome by adding a catalytic amount of nitrate salt, for example NaNO3 into the reaction. This stabilizes the Mn(NO3)2/TEMPO/PyCOOH catalyst and enables oxidation of various primary alcohols to the respective aldehydes using low catalyst loadings under ambient conditions. Secondary alcohols can be oxidized with a modified catalyst utilizing sterically accessible nitroxyl radical 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO) instead of TEMPO. At the end of the alcohol oxidation, pure carbonyl products and the reusable catalyst can be recovered simply by extracting with organic solvent and dilute aqueous acid, followed by evaporation of both phases.
Lagerblom, Kalle,Keskiv?li, Juha,Parviainen, Arno,Mannisto, Jere,Repo, Timo
p. 2908 - 2914
(2018/05/03)

On the Use of Polyelectrolytes and Polymediators in Organic Electrosynthesis
Although organic electrosynthesis is generally considered to be a green method, the necessity for excess amounts of supporting electrolyte constitutes a severe drawback. Furthermore, the employment of redox mediators results in an additional separation problem. In this context, we have explored the applicability of soluble polyelectrolytes and polymediators with the TEMPO-mediated transformation of alcohols into carbonyl compounds as a test reaction. Catalyst benchmarking based on cyclic voltammetry studies indicated that the redox-active polymer can compete with molecularly defined TEMPO species. Alcohol oxidation was also highly efficient on a preparative scale, and our polymer-based approach allowed for the separation of both mediator and supporting electrolyte in a single membrane filtration step. Moreover, we have shown that both components can be reused multiple times.
Schille, Benjamin,Giltzau, Niels Ole,Francke, Robert
supporting information
p. 422 - 426
(2018/02/21)

Stereoselective Synthesis of C1–C7 and C6–C22 Fragments of Phostriecin, Goniothalamines, and Their Analogues
The stereoselective synthesis of two fragments (C1–C7 and C6–C22) of the anti-tumor agent phostriecin has been achieved. The chiral hydroxy-vinyl-δ-lactone building block (fragment C1–C7) was subsequently utilized for the synthesis of 5-hydroxygoniothalamin, 5-acetoxygoniothalamin, and their derivatives.
Purushotham Reddy,Vasudeva Reddy,Sabitha, Gowravaram
p. 4389 - 4399
(2018/09/11)

Practical Aerobic Oxidation of Alcohols: A Ligand-Enhanced 2,2,6,6-Tetramethylpiperidine-1-oxy/Manganese Nitrate Catalyst System
A highly efficient, ligand-enhanced 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO)/Mn(NO3)2 catalyst system for the aerobic oxidation of alcohols is described. From the series of coordinating ligands studied herein, 2-picolinic acid (PyCOOH) improves the catalytic activity of TEMPO/Mn(NO3)2 remarkably. Under ambient air at room temperature in acetic acid, the ligand-enhanced catalyst converts aliphatic and benzylic primary alcohols that bear various functional groups into their respective aldehydes with near quantitative conversions. The applicability of the catalyst for convenient preparative synthesis was demonstrated by conducting oxidations on a gram scale. A change of TEMPO to the sterically less demanding 9-azabicyclo[3.3.1]nonane N-oxyl results in a Mn catalyst that is also able to oxidize secondary alcohols to ketones. Mechanistic studies showed that alcohols are oxidized by the oxoammonium cation derived from the nitroxyl radical. The active oxidant is regenerated by Mn(NO3)2, and this process is greatly promoted by the coordination of PyCOOH to Mn.
Lagerblom, Kalle,Lagerspets, Emi,Keskiv?li, Juha,Cook, Chris,Ekholm, Filip,Parviainen, Arno,Repo, Timo
p. 3880 - 3887
(2017/09/28)

Synthesis of α,β-unsaturated aldehydes as potential substrates for bacterial luciferases
Bacterial luciferase catalyzes the monooxygenation of long-chain aldehydes such as tetradecanal to the corresponding acid accompanied by light emission with a maximum at 490?nm. In this study even numbered aldehydes with eight, ten, twelve and fourteen carbon atoms were compared with analogs having a double bond at the α,β-position. These α,β-unsaturated aldehydes were synthesized in three steps and were examined as potential substrates in vitro. The luciferase of Photobacterium leiognathi was found to convert these analogs and showed a reduced but significant bioluminescence activity compared to tetradecanal. This study showed the trend that aldehydes, both saturated and unsaturated, with longer chain lengths had higher activity in terms of bioluminescence than shorter chain lengths. The maximal light intensity of (E)-tetradec-2-enal was approximately half with luciferase of P. leiognathi, compared to tetradecanal. Luciferases of Vibrio harveyi and Aliivibrio fisheri accepted these newly synthesized substrates but light emission dropped drastically compared to saturated aldehydes. The onset and the decay rate of bioluminescence were much slower, when using unsaturated substrates, indicating a kinetic effect. As a result the duration of the light emission is doubled. These results suggest that the substrate scope of bacterial luciferases is broader than previously reported.
Brodl, Eveline,Ivkovic, Jakov,Tabib, Chaitanya R.,Breinbauer, Rolf,Macheroux, Peter
p. 1487 - 1495
(2017/02/18)

Chemoenzymatic one-pot reaction of noncompatible catalysts: Combining enzymatic ester hydrolysis with Cu(i)/bipyridine catalyzed oxidation in aqueous medium
The combination of chemical catalysts and biocatalysts in a one-pot reaction has attracted considerable interest in the past years. However, since each catalyst requires very different reaction conditions, chemoenzymatic one-pot reactions in aqueous media remain challenging and are limited today to metal-catalysts that display high activity in aqueous media. Here, we report the first combination of two incompatible catalytic systems, a lipase based ester hydrolysis with a water-sensitive Cu/bipyridine catalyzed oxidation reaction, in a one-pot reaction in aqueous medium (PBS buffer). Key to the solution was the compartmentalization of the Cu/bipyridine catalyst in a core-shell like nanoparticle. We show the synthesis and characterization of the Cu/bipyridine functionalized nanoparticles and the application in the oxidation of allylic and benzylic alcohols in aqueous media. Furthermore, the work demonstrates the implementation of a one-pot reaction process with optimized reaction conditions involving a lipase (CAL-B) to hydrolyze various acetate ester substrates in the first step, followed by oxidation of the resulting alcohols to the corresponding aldehydes under aerobic conditions in aqueous media.
Sand, Henning,Weberskirch, Ralf
p. 33614 - 33626
(2017/07/12)

Selective Hydrogenation of Functionalized Alkynes to (E)-Alkenes, Using Ordered Alloys as Catalysts
Intermetallic Pd3Pb acts as a highly selective alkyne semihydrogenation catalyst that is greatly superior to the conventional Lindlar catalyst. Density functional theory (DFT) calculations demonstrate an ideal adsorption property of Pd3Pb, where the surface holds alkynes while releasing alkenes. A tandem catalytic system that is comprised of Pd3Pb/SiO2 for alkyne semihydrogenation and RhSb/SiO2 for alkene isomerization allows one-pot (E)-alkene synthesis from a functionalized alkyne, which is the first success using heterogeneous catalysts. A variety of functionalized alkynes with aldehyde, ketone, carboxylic acid, and ester moieties are hydrogenated into the corresponding (E)-alkene in good to excellent yields under 1 atm H2 at room temperature.
Furukawa, Shinya,Komatsu, Takayuki
p. 2121 - 2125
(2016/03/15)

Selective oxidation of styrene catalyzed by cerium-doped cobalt ferrite nanocrystals with greatly enhanced catalytic performance
The rare earth metal Ce-doped cobalt ferrite samples CexCo1?xFe2O4 (x?=?0.1, 0.3, 0.5) were prepared by the sol–gel autocombustion route. The as-prepared samples were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, ICP–atomic emission spectroscopy, and N2 physisorption. Their catalytic performance was evaluated in oxidation of styrene using hydrogen peroxide (30%) as oxidant. Compared with pristine CoFe2O4, the Ce-doped samples were found to be more efficient catalysts for the oxidation of styrene to benzaldehyde, with greatly enhanced catalytic performance. Especially, when Ce0.3Co0.7Fe2O4 was used as catalyst, 90.3% styrene conversion and 91.5% selectivity for benzaldehyde were obtained at 90?°C for 9?h reaction. The catalyst can be magnetically separated easily for reuse, and no obvious loss of activity was observed when it was reused in five consecutive runs.
Tong, Jinhui,Li, Wenyan,Bo, Lili,Wang, Huan,Hu, Yusen,Zhang, Zhixia,Mahboob, Abdulla
p. 474 - 481
(2016/11/18)

Method to oxidize alcohols selectively to aldehydes and ketones with heterogeneous supported ruthenium catalyst at room temperature in air and catalyst thereof
The present invention relates to a method for selectively oxidizing alcohol by using a heterogeneous catalyst for producing aldehyde and ketone in an organic synthesis process used in the laboratory and chemical industries, and a catalytic system thereof. The method can be used as an intermediate product for synthesizing medicine, scent, fragrance, and precise chemical products, and can use a heterogeneous catalyst at room temperature in air by using the catalytic system and producing alcohol and ketone.COPYRIGHT KIPO 2016
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(2016/10/07)

Iron-Catalysed Selective Aerobic Oxidation of Alcohols to Carbonyl and Carboxylic Compounds
A method for aerobic alcohol oxidation catalysed by Fe(NO3)3/2,2’-bipyridine/TEMPO has allowed highly selective conversion of primary alcohols into either aldehydes or carboxylic acids in one-step. The oxidation of primary alcohols proceeded selectively to aldehydes, as TEMPO was present in the reaction. Nevertheless, the aldehydes were further oxidized into carboxylic acids as the reaction time was extended. Detailed investigation of the reaction suggested, that the deoxygenation of TEMPO into TMP enabled the auto-oxidation of aldehydes to carboxylic acids, which was initially inhibited in the presence of TEMPO. The procedure was also efficient in oxidation of secondary alcohols when TEMPO was replaced by the less sterically hindered ABNO.
Lagerblom, Kalle,Wrigstedt, Pauli,Keskiv?li, Juha,Parviainen, Arno,Repo, Timo
p. 1160 - 1165
(2016/11/23)

1H-pyrrole-2,4-dicarbonyl-derivatives and their use as flavoring agents
The present invention primarily relates to 1H-pyrrole-2,4-dicarbonyl-derivatives of Formula (I) wherein R1, R2, R3, Z. Z' and J are as defined in the description, to mixtures thereof and to the use thereof as flavoring agents. The compounds in accordance with the present invention are suitable for producing, imparting, or intensifying an umami flavor. The invention further relates to flavoring mixtures, compositions for oral consumption as well as ready-to-eat, ready-to-use and semifinished products, comprising an effective amount of the compound of Formula (I) or of a mixture of compounds of Formula (I) and to specific methods for producing, imparting, modifying and/or intensifying specific flavor impressions.
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(2015/03/03)

Imidazo[1,2-a]pyridine-ylmethyl-derivatives and their use as flavoring agents
The present invention primarily relates to imidazo[1,2-a]pyridine-ylmethyl-derivatives of Formula (I) wherein R1, R2, X, W e J are as defined in the description, to mixtures thereof and to the use thereof as flavoring agents. The compounds in accordance with the present invention are suitable for producing, imparting, or intensifying an umami flavor. The invention further relates to flavoring mixtures, compositions for oral consumption as well as ready-to-eat, ready-to-use and semifinished products, comprising an effective amount of the compound of Formula (I) and to specific methods for producing, imparting, modifying and/or intensifying specific flavor impressions.
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(2015/03/03)

Tandem Benzylic Oxidation/Dihydroxylation of α-Vinyl- and α-Alkenylbenzyl Alcohols
A de novo tandem benzylic oxidative dihydroxylation of α-vinyl- and α-alkenylbenzyl alcohols has been developed to give α,β-dihydroxypropiophenones (=2,3-dihydroxy-1-phenylpropan-1-ones) and α,β-dihydroxyalkyl phenones. This method was shown to be substrate-selective and specific for the oxidation of benzylic alcohols.
Fernandes, Rodney A.,Kattanguru, Pullaiah
p. 92 - 107
(2015/10/19)

A TEMPO-free copper-catalyzed aerobic oxidation of alcohols
The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols.
Xu, Boran,Lumb, Jean-Philip,Arndtsen, Bruce A.
supporting information
p. 4208 - 4211
(2015/04/14)

METHOD FOR PRODUCING α,β-UNSATURATED CARBONYL COMPOUNDS
PROBLEM TO BE SOLVED: To provide a simple and efficient, novel method for producing α,β-unsaturated carbonyl compounds, which can provide α,β-unsaturated carbonyl compounds from allyl alcohols with high yields under a mild reaction condition, and has extremely little influence and toxicity on the environment and the human body. SOLUTION: Provided is a method for producing α,β-unsaturated carbonyl compounds, the method comprising reacting allyl alcohols and hydrogen peroxide to carbonylate alcohol portions to produce corresponding α,β-unsaturated carbonyl compounds. As a reaction catalyst, there are used an Fe(II) or Fe(III) salt soluble in water or an organic solvent, and at least one picolinic acid selected from 2-picolinic acid and 6-C1-4 alkyl-2-picolinic acid in coexistence in a ratio of 1:1 to 1:4. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0037-0038

(2016/12/26)

Crystal Structure and Catalytic Behavior in Olefin Epoxidation of a One-Dimensional Tungsten Oxide/Bipyridine Hybrid
The tungsten oxide/2,2′-bipyridine hybrid material [WO3(2,2′-bpy)]·nH2O (n = 1-2) (1) has been prepared in near quantitative yield by the reaction of H2WO4, 2,2′-bpy, and H2O in the mole ratio of ca. 1:2:700 at 160°C for 98 h in a rotating Teflon-lined digestion bomb. The solid-state structure of 1 was solved and refined through Rietveld analysis of high-resolution synchrotron X-ray diffraction data collected for the microcrystalline powder. The material, crystallizing in the orthorhombic space group Iba2, is composed of a one-dimensional organic-inorganic hybrid polymer, ∞1[WO3(2,2′-bpy)], topologically identical to that found in the previously reported anhydrous phases [MO3(2,2′-bpy)] (M = Mo, W). While in the latter the N,N′-chelated 2,2′-bpy ligands of adjacent corner-shared {MO4N2} octahedra are positioned on the same side of the 1D chain, in 1 the 2,2′-bpy ligands alternate above and below the chain. The catalytic behavior of compound 1 for the epoxidation of cis-cyclooctene was compared with that for several other tungsten- or molybdenum-based (pre)catalysts, including the hybrid polymer [MoO3(2,2′-bpy)]. While the latter exhibits superior performance when tert-butyl hydroperoxide (TBHP) is used as the oxidant, compound 1 is superior when aqueous hydrogen peroxide is used, allowing near-quantitative conversion of the olefin to the epoxide. With H2O2, compounds 1 and [MoO3(2,2′-bpy)] act as sources of soluble active species, namely, the oxodiperoxo complex [MO(O2)2(2,2′-bpy)], which is formed in situ. Compounds 1 and [WO(O2)2(2,2′-bpy)] (2) were further tested in the epoxidation of cyclododecene, trans-2-octene, 1-octene, (R)-limonene, and styrene. The structure of 2 was determined by single-crystal X-ray diffraction and found to be isotypical with the molybdenum analogue.
Amarante, Tatiana R.,Antunes, Margarida M.,Valente, Anabela A.,Paz, Filipe A. Almeida,Pillinger, Martyn,Gon?alves, Isabel S.
p. 9690 - 9703
(2015/11/03)

Lipid-derived aldehyde degradation under thermal conditions
Nucleophilic degradation produced by reactive carbonyls plays a major role in food quality and safety. Nevertheless, these reactions are complex because reactive carbonyls are usually involved in various competitive reactions. This study describes the thermal degradation of 2-alkenals (2-pentenal and 2-octenal) and 2,4-alkadienals (2,4-heptadienal and 2,4-decadienal) in an attempt to both clarify the stability of aldehydes and determine new compounds that might also play a role in nucleophile/aldehyde reactions. The obtained results showed that alkenals and alkadienals decomposed rapidly in the presence of buffer and air to produce formaldehyde, acetaldehyde, and the aldehydes corresponding to the breakage of the carboncarbon double bonds: propanal, hexanal, 2-pentenal, 2-octenal, glyoxal, and fumaraldehyde. The activation energy of double bond breakage was relatively low (～25 kJ/mol) and the yield of alkanals (10-18%) was higher than that of 2-alkenals (～1%). All these results indicate that these reactions should be considered in order to fully understand the range of nucleophile/aldehyde adducts produced.
Zamora, Rosario,Navarro, José L.,Aguilar, Isabel,Hidalgo, Francisco J.
p. 89 - 96
(2015/02/19)

Bipyridine-functionalized amphiphilic block copolymers as support materials for the aerobic oxidation of primary alcohols in aqueous media
Amphiphilic block copolymers with 4-methoxy-4′-alkoxybipyridine ligands in the hydrophobic block were synthesized by cationic ring-opening polymerization. The bipyridine moiety was either introduced directly as a 2-oxazoline monomer (P1) or by polymer-analogous coupling to a precursor poly(2-oxazoline) with chloropentyl side chains (PP2-PP7) to prepare the polymer ligands (P2-P7). The polymers were characterized by NMR and SEC measurements to determine polymer composition, molar masses and polydispersities. In water, these polymers form micelles with cmc values ranging from 1.8 to 22 μmol l-1. SAXS and DLS measurements exhibited spherical particles with particle sizes of 8 to 21 nm. Polymers P1-P7 were finally utilized to carry out the aerobic oxidation of primary alcohols, including allylic, benzylic, and aliphatic derivatives at room temperature (T = 20°C) and ambient air in aqueous media indicating higher activities for P2-P7 compared to P1 as a consequence of the different preparation methods. Moreover, product isolation and catalyst recycling can be easily accomplished by solvent extraction five times without significant loss of activity.
Sand, Henning,Weberskirch, Ralf
p. 38235 - 38242
(2015/06/30)

Selective oxidations of activated alcohols in water at room temperature
Allylic and benzylic alcohols can be selectively oxidized to their corresponding aldehydes or ketones in water containing nanoreactors composed of the designer surfactant TPGS-750-M. The oxidation relies on catalytic amounts of CuBr, bpy, and TEMPO, with N-methyl-imidazole; air is the stoichiometric oxidant. the Partner Organisations 2014.
Lipshutz,Hageman,Fennewald,Linstadt,Slack,Voigtritter
supporting information
p. 11378 - 11381
(2014/11/08)

An expedient osmium(vi)/K3Fe(CN)6-mediated selective oxidation of benzylic, allylic and propargylic alcohols
A chemoselective osmium(vi) catalyzed oxidation of benzylic, allylic and propargylic alcohols using K3Fe(CN)6as a secondary oxidant is described. This protocol is operationally simple and exhibits excellent chemoselectivity favouring the oxidation of benzylic alcohols over the aliphatic alcohols. A larger scale reaction was also found to be compatible. This journal is
Fernandes, Rodney A.,Bethi, Venkati
p. 40561 - 40568
(2015/02/18)

Chemoselective hydrogen peroxide oxidation of allylic and benzylic alcohols under mild reaction conditions catalyzed by simple iron-picolinate complexes
Chemoselective oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds proceeded efficiently using hydrogen peroxide with iron-picolinate catalysts. The in situ generated [Fe(Me-Pic)3] (Me-Pic = 6-methylpicolinate) catalyzed oxidation of the alcohol moiety of primary allylic alcohols while the [Fe(Pic)3] (Pic = picolinate) and [Fe(Me-Pic)2(Pic)] did not show sufficient catalytic activity. the Partner Organisations 2014.
Tanaka, Shinji,Kon, Yoshihiro,Nakashima, Takuya,Sato, Kazuhiko
p. 37674 - 37678
(2014/11/07)

Chemoselective hydrogen peroxide oxidation of allylic and benzylic alcohols under mild reaction conditions catalyzed by simple iron-picolinate complexes
Chemoselective oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds proceeded efficiently using hydrogen peroxide with iron-picolinate catalysts. The in situ generated [Fe(Me-Pic)3] (Me-Pic = 6-methylpicolinate) catalyzed oxidation of the alcohol moiety of primary allylic alcohols while the [Fe(Pic)3] (Pic = picolinate) and [Fe(Me-Pic)2(Pic)] did not show sufficient catalytic activity. This journal is
Tanaka, Shinji,Kon, Yoshihiro,Nakashima, Takuya,Sato, Kazuhiko
p. 37674 - 37678
(2014/12/11)

METHOD FOR OXIDIZING ALCOHOLS
A method for oxidizing an alcohol, wherein oxidation is performed in the presence of a compound represented by the following formula (I) and a bulk oxidant, which enables efficient oxidation of secondary alcohols as well as primary alcohols, and can attain high reaction efficiency even when air is used as a bulk oxidant.
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Paragraph 0127; 0128

(2013/06/05)

Microwave-assisted synthesis of N -isobutyl-4,5-epoxy-2(E)-decenamide
A new and efficient synthesis of a naturally occurring amide alkaloid, N-isobutyl-4,5-epoxy-2(E)-decenamide isolated from the roots of Piper nigrum has been described involving a total of nine steps. Octanal and 2-bromoacetic acid have been used as the starting materials.
Gupta, Neeraj,Kaur, Manvinder,Shallu,Gupta, Neeru,Kad, Goverdhan Lal,Singh, Jasvinder
p. 548 - 553
(2013/05/21)

Remarkable solvent, porphyrin ligand, and substrate effects on participation of multiple active oxidants in manganese(III) porphyrin catalyzed oxidation reactions
The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron-withdrawing and -donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1-octene, and ethylbenzene in various solvent systems, namely, toluene, CH 2Cl2, CH3CN, and H2O/CH 3CN (1:4). With an increase in the concentration of the easy-to-oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1 a) with electron-donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)Mn-OOC(O)R] species 2 a is the major active species. When the substrate was changed from the easy-to-oxidize one (cyclohexene) to difficult-to-oxidize ones (1-octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F20TPP)Mn-OOC(O)R] species 2 b generated from the reaction of [(F20TPP)MnCl] (1 b) with electron-withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)Mn-OOR] 2 a) depending on the concentration of the easy-to-oxidize substrate cyclohexene in all aprotic solvent systems except for CH3CN, whereas MnV=O species is the major active oxidant in the protic solvent system. With difficult-to-oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1-octene in toluene, indicating that a MnV=O intermediate generated from the heterolytic cleavage of 2 b becomes a major reactive species. We also studied the competitive epoxidations of cis-2-octene and trans-2-octene with two manganese(III) porphyrin complexes by meta-chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis- to trans-2-octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further supporting the contention that the reactions of manganese porphyrin complexes with peracids generate multiple reactive oxidizing intermediates. Copyright
Hyun, Min Young,Jo, Young Dan,Lee, Jun Ho,Lee, Hong Gyu,Park, Hyun Min,Hwang, In Hong,Kim, Kyeong Beom,Lee, Suk Joong,Kim, Cheal
supporting information
p. 1810 - 1818
(2013/03/13)

Selective aerobic oxidation of activated alkanes with MOFs and their use for epoxidation of olefins with oxygen in a tandem reaction
MOFs with Cu2+ centers linked to four nitrogen atoms from azaheterocyclic compounds, i.e., pyrimidine [Cu(2-pymo)2] and imidazole [Cu(im)2], are active catalysts for aerobic oxidation of activated alkanes, such as tetralin, cumene and ethylbenzene. Differences in activity among the two MOFs appear to be related to differences in their ability to decompose the hydroperoxide and to coordinate to the resulting radical OH species. Copper ions in [Cu(im)2] can coordinate by expanding their coordination sphere from 4 to 5 in a reversible way, while in the case of [Cu(2-pymo)2] it results in a displacement of one of the pyrimidine ligands. The MOFs can be used in combination with a silylated Ti-MCM-41 to catalyze the epoxidation of olefins with oxygen by means of a tandem reaction in which the MOF produces cumene hydroperoxide, which is used by Ti-MCM-41 to epoxidize the olefin. The Royal Society of Chemistry 2013.
Luz,Leon,Boronat,Llabres I Xamena,Corma
p. 371 - 379
(2013/03/14)

Dispersed Ru nanoclusters transformed from a grafted trinuclear Ru complex on SiO2 for selective alcohol oxidation
Ru nanoclusters (average diameter = 1.3 ± 0.3 nm) were successfully prepared by using a Ru3 cluster Ru3O(CH 3COO)6(H2O)3·(CH 3COO) grafted on a pyridine-functionalized SiO2 surface. The pyridine moiety dispersed on the SiO2 surface spread the Ru 3 cluster, controlling its surface density, and the nanoclusterization of the Ru cluster proceeded on the surface. The structures of the Ru nanoclusters were characterized by means of elemental analysis; thermogravimetric analysis; FT-IR, UV/vis, and solid-state NMR spectroscopy; BET analysis; X-ray photoelectron spectroscopy; X-ray diffraction; transmission electron microscopy; and Ru K-edge X-ray absorption fine structure analysis. It was found that the catalytic activity for the selective oxidation of alcohol to the corresponding aldehyde using O2 highly depended on the dispersion and structures of the Ru particles, and the Ru nanocluster was found to be efficient in the selective oxidation of a variety of alcohols.
Muratsugu, Satoshi,Lim, Min Hwee,Itoh, Takahiro,Thumrongpatanaraks, Wipavee,Kondo, Mio,Masaoka, Shigeyuki,Andy Hor,Tada, Mizuki
p. 12611 - 12619
(2013/09/02)

Oxidation of alcohols to carbonyl compounds with diisopropyl azodicarboxylate catalyzed by nitroxyl radicals
A nitroxyl-radical-catalyzed oxidation of alcohols using diisopropyl azodicarboxylate (DIAD) as the terminal oxidantis reported. A variety of primary and secondary alcohols including aliphatic, benzylic, and allylic alcohols are efficiently oxidized to their corresponding aldehydes and ketones without overoxidation to carboxylic acid. 1,2-Diols are oxidized to hydroxyl ketones or diketones depending on the amount of DIAD used.
Hayashi, Masaki,Shibuya, Masatoshi,Iwabuchi, Yoshiharu
experimental part
p. 3005 - 3009
(2012/05/04)

Efficient and selective oxidation of primary and secondary alcohols using an iron(III)/phenanthroline complex: Structural studies and catalytic activity
An efficient catalytic system for the oxidation of alcohols has been developed by using iron(III) catalyst [Fe(phen)2Cl 2]NO3 (1) (phen = 1,10-phenanthroline) and H 2O2 as terminal oxidant. A series of primary and secondary alcohols were oxidized into aldehydes and ketones in good yields and excellent selectivities after a short reaction time. The mononuclear iron(III) complex [Fe(phen)2Cl2]NO3 was characterized by several independent methods. The X-ray structure shows distorted octahedral geometry around the FeIII center, which is in a high-spin state (S = 5/2) according to Moessbauer study. Copyright
Biswas, Bhaskar,Kole, Niranjan,Al-Hunaiti, Afnan,Raeisaenen, Minna T.,Ansalone, Simone,Leskelae, Markku,Repo, Timo,Chen, Yen-Tung,Tsai, Hui-Lien,Naik, Anil D.,Railliet, Antoine P.,Garcia, Yann,Ghosh, Rajarshi
p. 4479 - 4485,7
(2020/08/24)

Sequencing cross-metathesis and non-metathesis reactions to rapidly access building blocks for synthesis
The olefin cross-metathesis reaction has been sequenced with four common organic transformations in a one- or two-pot manner to rapidly access useful building blocks. Those reactions are: (1) phosphorus-based olefination (e.g., Wittig and Horner-Wadsworth-Emmons); (2) hydride reduction; (3) Evans propionate aldol reaction; (4) Brown allyl- and Roush crotyl-boration. The products of these reactions include stereodefined 2,4-dienoates, trans allylic alcohols, syn-propionate aldols, and chiral non-racemic homoallylic alcohols, respectively. Many of these intermediates have been carried further to natural products, demonstrating the utility of the methodology.
Sirasani, Gopal,Paul, Tapas,Andrade, Rodrigo B.
experimental part
p. 2197 - 2205
(2011/04/22)

Structure and characteristics of chitosan cobalt-containing hybrid systems, the catalysts of olefine oxidation
Cobalt-containing hybrid organo-inorganic materials based on the chitosan-SiO2, chitosan-Al2O3, and chitosan-cellulose systems were obtained. The surface structure and processes that occur during the formation of metal-containing materials, the catalytic properties of which were studied in the oxidation reactions of alkene, were investigated by EPR spectroscopy using a stable pH-sensitive nitroxyl radical, 4-dimethylamino-2-ethyl-5,5-dimethyl-2-(pyridin-4-yl)-2,5-dihydro-1H-imidazole- 1-oxyl, as the adsorbed probe molecules.
Mekhaev,Pestov,Molochnikov,Kovaleva,Pervova,Yaltuk, Yu. G.,Grigor'Ev,Kirilyuk
experimental part
p. 1155 - 1161
(2011/08/05)

REGENERATION OF A HYDROFORMYLATION CATALYST DURING HYDROFORMYLATION
A method for hydroformylating or hydrocarbonylating a substrate having a carbon-carbon double or triple bond or both is described. The method comprises exposing the substrate to a hydroformylation catalyst under an atmosphere comprising carbon monoxide and hydrogen in the presence of a regeneration reagent so as to form a product. The regeneration reagent is such that it is capable of at least partially reversing poisoning of the hydroformylation catalyst by a diene or an alkyne or both.
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Page/Page column 16-17

(2011/04/14)

Effect of oxidized arachidonic acid and hexanal on the mouse taste perception of bitterness and umami
The oxidization of fatty acids generates many volatile compounds forming an aroma, but little is known whether mammals use gustatory sense to detect the oxidized products as a taste or only use olfactory sense to detect as an aroma. We examined in this study the effect of aqueous extracts of the compounds from autoxidized arachidonic acid (AA) ethyl ester or hexanal which is the predominant component generated from oxidized AA by the anosmic mouse licking performance to a tastant. The addition of the water extract from oxidized AA or hexanal to a quinine hydrochloride (QHC1) solution decreased the anosmic mice licking frequency at several concentrations of QHC1. Hexanal also reduced the licking frequency of anosmic mice conditioned to avoid MSG at several concentrations of monosodium glutamate (MSG). These results suggest that hexanal would affect mouse taste perception to QHC1 and MSG via the gustatory sensation.
Yamaguchi, Susumu,Fujiwara, Hidenori,Tashima, Ikukazu,Iwanaga, Daigo,Ushio, Hideki
experimental part
p. 1884 - 1890
(2011/06/17)

Exploring the versatility of the Johnson-Claisen rearrangement: access to functionally versatile δ-ethoxycarbonyl-α,β-unsaturated nitriles
A practical entry into δ-ethoxycarbonyl-α,β-unsaturated nitriles is described. α,β-Unsaturated aldehydes were converted to cyanohydrins, by employing either KCN in aqueous acid, or by using TMSCN with catalytic K2CO3, followed by acid hydrolysis of the TMS ether. These cyanohydrins underwent a Claisen rearrangement employing a modified Johnson-Claisen protocol to yield unsaturated nitriles in good yields and with moderate E/Z selectivity.
Cosgrove, Kelly L.,McGeary, Ross P.
scheme or table
p. 3050 - 3057
(2010/06/16)

Biooxidation of Primary Alcohols to Aldehydes through Hydrogen Transfer Employing Janibacter terrae
Chemoselective oxidations still represent a challenge for chemists. Lyophilized cells of Janibacter terrae were employed for the chemoselective oxidation of primary alcohols to the corresponding aldehydes by hydrogen transfer with the use of acetaldehyde as the hydrogen acceptor. Secondary alcohol moieties were transformed at a much slower rate. The substrate spectrum encompasses substituted benzyl alcohols, whereby substrates with a substituent in the meta position were well tolerated, whereas only very small substituants were tolerated in the ortho position. Furthermore, nalkanols and allylic alcohols were transformed with good conversions. The biocatalyst was compatible with DMSO as a water miscible organic solvent up to 30 % v/v.
Orbegozo, Thomas,De Vries, Johannes G.,Kroutil, Wolfgang
experimental part
p. 3445 - 3448
(2010/09/05)

PpoC from Aspergillus nidulans is a fusion protein with only one active haem
In Aspergillus nidulans Ppos [psi (precocious sexual inducer)-producing oxygenases] are required for the production of so-called psi factors, compounds that control the balance between the sexual and asexual life cycle of the fungus. The genome of A. nidulans harbours three different ppo genes: ppoA, ppoB and ppoC. For all three enzymes two different haem-containing domains are predicted: a fatty acid haem peroxidase/ dioxygenase domain in the N-terminal region and a P450 haem-thiolate domain in the C-terminal region. Whereas PpoA was shown to use both haem domains for its bifunctional catalytic activity (linoleic acid 8-dioxygenation and 8-hydroperoxide isomerization), we found that PpoC apparently only harbours a functional haem peroxidase/dioxygenase domain. Consequently, we observed that PpoC catalyses mainly the dioxygenation of linoleic acid (18:2Δ 9Z,12Z), yielding 10-HPODE (10-hydroperoxyoctadecadienoic acid). No isomerase activity was detected. Additionally, 10-HPODE was converted at lower rates into 10-KODE (10-keto-octadecadienoic acid) and 10-HODE (10-hydroxyoctadecadienoic acid). In parallel, decomposition of 10-HPODE into 10-ODA (10-octadecynoic acid) and volatile C-8 alcohols that are, among other things, responsible for the characteristic mushroom flavour. Besides these principle differences we also found that PpoA and PpoC can convert 8-HPODE and 10-HPODE into the respective epoxy alcohols: 12,13-epoxy-8-HOME (where HOME is hydroxyoctadecenoic acid) and 12,13-epoxy-10-HOME. By using site-directed mutagenesis we demonstrated that both enzymes share a similar mechanism for the oxidation of 18:2Δ9Z,12Z; they both use a conserved tyrosine residue for catalysis and the directed oxygenation at the C-8 and C-10 is most likely controlled by conserved valine/leucine residues in the dioxygenase domain. The Authors Journal compilation
Brodhun, Florian,Schneider, Stefan,Goebel, Cornelia,Hornung, Ellen,Feussner, Ivo
experimental part
p. 553 - 565
(2011/02/23)

New route for the synthesis of benzimidazoles by a one-pot multistep process with mono and bifunctional solid catalysts
One-pot multistep reactions involving a new environmentally friendly catalytic procedure have been developed for the synthesis of benzimidazoles. Benzimidazole derivatives with biological and pharmaceutical interest have been prepared by a one-pot four step process with a solid catalyst containing basic and oxidation sites. The four steps refer to: (a) oxidation of the alcohol; (b) cyclocondensation of the aldehyde formed with ortho-phenylenediamines, (c) oxidation of the carbon-nitrogen bond, (d) N-alkylation reaction. The process is illustrated by the synthesis of 1,2-disubstituted benzimidazole derivative with antiviral activity.
Ruiz, Violeta R.,Corma, Avelino,Sabater, María J.
experimental part
p. 730 - 735
(2010/09/11)

Thieme chemistry journal awardees - Where are they now? aldol synthesis by anti-markovnikov hydration of propargyloxy substrates: Feasibility, stereospecifity, and reiterative alkynylation-hydration
Aldol derivatives have been synthesized by redox-neutral catalytic anti-Markovnikov hydration of propargyloxy sub-strates. A reiterative sequence of aldehyde alkynylation and alkyne hydration leads to 1,3-polyol derivatives. Georg Thieme Verlag Stuttgart.
Hintermann, Lukas,Kribber, Thomas,Labonne, Aurélie,Paciok, Eva
scheme or table
p. 2412 - 2416
(2009/12/08)

Model studies on the degradation of phenylalanine initiated by lipid hydroperoxides and their secondary and tertiary oxidation products
The reaction of methyl 13-hydroperoxyoctadeca-9,11-dienoate (MeLOOH), methyl 13-hydroperoxyoctadeca-9,11,15-trienoate (MeLnOOH), methyl 13-hydroxyoctadeca-9,11-dienoate (MeLOH), methyl 13-oxooctadeca-9,11-dienoate (MeLCO), methyl 9,10-epoxy-13-hydroxy-11-octadecenoate (Me-LEPOH), and methyl 9,10-epoxy-13-oxo-11-octadecenoate (MeLEPCO) with phenylalanine was studied to determine the comparative reactivity of primary, secondary, and tertiary lipid oxidation products in the Strecker degradation of amino acids. All assayed lipids were able to degrade the amino acid to a high extent, although the lipid reactivity decreased slightly in the following order: MeLEPCO ≥ MeLCO > MeLEPOH ≥ MeLOH > MeLOOH ≈ MeLnOOH. These data confirmed the ability of many lipid oxidation products to degrade amino acids by a Strecker-type mechanism and suggested that, once the lipid oxidation is produced, a significant Strecker degradation of surrounding amino acids should be expected. The contribution of different competitive mechanisms to this degradation is proposed, among which the conversion of the different lipid oxidation products assayed into the most reactive MeLEPCO and the fractionation of long-chain primary and secondary lipid oxidation products into short-chain aldehydes are likely to play a major role.
Zamora, Rosario,Gallardo, Emerenciana,Hidalgo, Francisco J.
experimental part
p. 7970 - 7975
(2010/03/30)

Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols: The molecular reaction mechanism
As previously reported for for solventless reactions, gold nanoparticles supported on ceria are also excellent general heterogeneous catalysts for the aerobic oxidations of alcohols in organic solvents. Among organic solvents it was found that toluene is a convenient one. A systematic study on the influence of the particle size and gold content on the support has established that the activity correlates linearly with the total number of external gold atoms, and with the surface coverage of the support. Amongst catalysts with different supports, but similar gold particle size and content, gold on ceria exhibits the highest activity. By means of a kinetic study (influence of σ+ parameter, kinetic isotopic effect, temperature, alcohol concentration and oxygen pressure) a mechanistic proposal consisting of the formation of metalalcoholate, β-hydride shift from carbon to metal and M-H oxidation has been proposed that explains all experimental results.
Abad, Alberto,Corma, Avelino,Garcia, Hermenegildo
p. 212 - 222
(2008/09/18)

Evaluation of the formation and stability of hydroxyalkylsulfonic acids in wines
The presence of carbonyl compounds (CCs) in wines has sparked the interest of researchers in several countries. The quantification of some of these compounds has been used as a parameter of quality for many fermented beverages. Although present in minute quantities (except for acetaldehyde), they have a strong olfactory impact. In addition, the CCs found in wines have a strong affinity for bisulfite and can form stable adducts, which will also interfere in the characteristics of aroma. The greatest challenge, however, is to predict which CCs have the strongest affinity for S(IV) and what conditions favor this interaction. To better understand the reaction of CC-bisulfite adduct formation (HASA), this study has evaluated the profile of 22 CCs in a "synthetic wine" containing bisulfite and in 10 real samples of different wines from the Sao Francisco Valley, northeastern Brazil. On the basis of principal component analysis (PCA) and dissociation constants, the results revealed that aliphatic aldehydes form adducts with S(IV), whereas ketones, cyclic aldehydes, and trans-alkenes interact weakly and are found predominantly in their free form. These results revealed also that pH 10 and 11 were defined as the most appropriate for CC-SO2 adduct dissociation, and the total CCs were quantified reliably.
De Azevedo, Luciana C.,Reis, Marina M.,Motta, Luiz F.,Da Rocha, Gisele O.,Silva, Luciana A.,De Andrade, Jailson B.
scheme or table
p. 8670 - 8680
(2009/09/28)

Aerobic alcohol oxidation catalyzed by a new, oxygen-bridged heterometallic compound [PPh4][Ru(N)Me2(μ2-O)2Pd((-)-sparteine)]
The reaction between the new hydroxy compound [PPh4][Ru(N)(OH)2Me2] and Pd(OSiMe3)2((-)-sparteine) produces (Me3Si)2O, H2O and a new heterobimetallic compound [PPh4][Ru(N)Me2(μ2-O)2Pd((-)-sparteine)] in good yield. The Ru/Pd bimetallic compound catalyzes the oxidation of aryl and allyl alcohols to the corresponding carbonyl compound in air and the rearrangement of allylic alcohols unsaturated aldehydes. It also oxidizes PPh3 to O-PPh3 under O2.
Kuiper, Jesse L.,Shapley, Patricia A.
p. 1653 - 1660
(2007/10/03)

Oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds with aqueous hydrogen peroxide under organic solvent-free conditions
Allylic alcohols are chemoselectively oxidized to α,β- unsaturated carbonyl compounds in high yield with aqueous H2O 2 in the presence of Pt black catalyst under organic solvent-free conditions. The catalyst is easily recyclable and effective for at least 7 cycles. The Royal Society of Chemistry.
Kon, Yoshihiro,Usui, Yoko,Sato, Kazuhiko
p. 4399 - 4400
(2008/04/01)