Palladium Assisted Oxidation of Cyclopentene by Molecular Oxygen

Takehira, Katsuomi; Hayakawa, T.; Orita, Hideo

doi:10.1246/cl.1985.1835

Cited by 27 publications

(10 citation statements)

References 7 publications

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“…30 Takehira et al also proposed the formation of Pd(II)-OOH species from palladium, ethanol, and oxygen. 31 Recently, many groups have reported that the Pd(II)-OOH species was believed to be acting as the key intermediate. Thus, H 2 O 2 was produced in the catalytic cycle.…”

Section: Resultsmentioning

confidence: 99%

Supercritical carbon dioxide and poly(ethylene glycol): an environmentally benign biphasic solvent system for aerobic oxidation of styrene

Wang

Cai

et al. 2007

Green Chem.

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Aerobic oxidation of styrene catalyzed by PdCl 2 /CuCl can be smoothly performed in the supercritical carbon dioxide and poly(ethylene glycol) biphasic system. A high conversion of styrene and yield of acetophenone were obtained in the presence of a relatively low catalyst loading. This environmentally benign biphasic catalytic system can be applied to the Wacker oxidation of various alkenes. Furthermore, the PdCl 2 -mediated oxidation of styrene was preferentially converted into benzaldehyde using a biphasic scCO 2 /PEG system. The PEG could effectively immobilize and stabilize the catalysts. The present biphasic system could facilitate product separation and catalyst recycling. The effects of the reaction parameters such as solvent and CO 2 pressure were also investigated in detail.

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Section: Resultsmentioning

confidence: 99%

Supercritical carbon dioxide and poly(ethylene glycol): an environmentally benign biphasic solvent system for aerobic oxidation of styrene

Wang

Cai

et al. 2007

Green Chem.

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“…46 Finally, because the Pd 0 intermediate in Path B cannot easily account for the formation of olefin isomer cis-2-d-55, we favor syn oxypalladation Path C. The remaining steps of the catalytic cycle involve reprocessing of Pd(II) by molecular oxygen. On the basis of earlier work by Murahashi and Takehira,3g,47 Uemura has proposed that this occurs by insertion of O 2 directly into the [Pd II ]-H to form a Pd-hydroperoxide intermediate. 17a Stahl has elaborated the details of a mechanism for aerobic oxidation catalysis by Pd-(II) that entails reductive elimination of HX from [Pd II ]-H to form Pd(0), which is then oxidized by O 2 in the formation of a Pd-peroxo intermediate.…”

Section: A R T I C L E Smentioning

confidence: 99%

Oxidative Cyclizations in a Nonpolar Solvent Using Molecular Oxygen and Studies on the Stereochemistry of Oxypalladation

2005

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Oxidative cyclizations of a variety of heteroatom nucleophiles onto unactivated olefins are catalyzed by palladium(II) and pyridine in the presence of molecular oxygen as the sole stoichiometric oxidant in a nonpolar solvent (toluene). Reactivity studies of a number of N-ligated palladium complexes show that chelating ligands slow the reaction. Nearly identical conditions are applicable to five different types of nucleophiles: phenols, primary alcohols, carboxylic acids, a vinylogous acid, and amides. Electron-rich phenols are excellent substrates, and multiple olefin substitution patterns are tolerated. Primary alcohols undergo oxidative cyclization without significant oxidation to the aldehyde, a fact that illustrates the range of reactivity available from various Pd(II) salts under differing conditions. Alcohols can form both fused and spirocyclic ring systems, depending on the position of the olefin relative to the tethered alcohol; the same is true of the acid derivatives. The racemic conditions served as a platform for the development of an enantioselective reaction. Experiments with stereospecifically deuterated primary alcohol substrates rule out a "Wacker-type" mechanism involving anti oxypalladation and suggest that the reaction proceeds by syn oxypalladation for both mono-and bidentate ligands. In contrast, cyclizations of deuterium-labeled carboxylic acid substrates undergo anti oxypalladation.

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“…Takehira and coworkers reported the oxidation of cyclohexene to cyclohexanone with cooxidation of ethanol to acetaldehyde (Figure 4a). 52 Further, a system was developed, which utilizes CuCl 2 in addition to palladium (Figure 4b). 53,54 The authors suggest that a heterobimetallic Pd–Cu(I) species is formed and that the role of copper is as a transient oxygen carrier that facilitates the generation of a Pd–OOH species (Figure 4c).…”

Section: Peroxide-mediated Wacker-type Oxidationsmentioning

confidence: 99%

“…52–54 b) The reaction is proposed to occur via alcohol oxidation to provide a Pd–H, into which molecular oxygen can insert. c) The authors suggest an operative Pd–Cu heterobimetallic species.…”

Section: Figurementioning

confidence: 99%

ChemInform Abstract: Peroxide‐Mediated Wacker Oxidations for Organic Synthesis

Michel

Sigman

2012

ChemInform

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Palladium Assisted Oxidation of Cyclopentene by Molecular Oxygen

Abstract: Dichlorobis(N,N-dialkylacetamide)palladium(II) complex catalyzes the oxidation of cyclopentene to cyclopentanone by molecular oxygen in alcoholic solvent, in which one atom of molecular oxygen in incorporated.

Cited by 27 publications

References 7 publications

Supercritical carbon dioxide and poly(ethylene glycol): an environmentally benign biphasic solvent system for aerobic oxidation of styrene

Supercritical carbon dioxide and poly(ethylene glycol): an environmentally benign biphasic solvent system for aerobic oxidation of styrene

Oxidative Cyclizations in a Nonpolar Solvent Using Molecular Oxygen and Studies on the Stereochemistry of Oxypalladation

ChemInform Abstract: Peroxide‐Mediated Wacker Oxidations for Organic Synthesis

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