Pd-mediated epoxidation of olefins

Мuzart, Jacques

doi:10.1016/j.molcata.2007.06.006

Cited by 37 publications

(16 citation statements)

References 100 publications

(93 reference statements)

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“…[78][79][80][81][82][83] Undoubtedly, when compared with bare Pd, the Pd-based bimetallic nanostructures should possess different features such as shapes and surface structures, allowing for tuning of their surface charge state and molecular reactant adsorption. Here we specifi cally highlight the tuning of surface charge state by interfacial polarization, which has not been previously investigated for oxygen activation.…”

Section: Integrating Metallic Pd With Other Metalsmentioning

confidence: 99%

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Palladium‐Based Nanomaterials: A Platform to Produce Reactive Oxygen Species for Catalyzing Oxidation Reactions

et al. 2015

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Oxidation reactions by molecular oxygen (O2 ) over palladium (Pd)-based nanomaterials are a series of processes crucial to the synthesis of fine chemicals. In the past decades, investigations of related catalytic materials have mainly been focused on the synthesis of Pd-based nanomaterials from the angle of tailoring their surface structures, compositions and supporting materials, in efforts to improve their activities in organic reactions. From the perspective of rational materials design, it is imperative to address the fundamental issues associated with catalyst performance, one of which should be oxygen activation by Pd-based nanomaterials. Here, the fundamentals that account for the transformation from O2 to reactive oxygen species over Pd, with a focus on singlet O2 and its analogue, are introduced. Methods for detecting and differentiating species are also presented to facilitate future fundamental research. Key factors for tuning the oxygen activation efficiencies of catalytic materials are then outlined, and recent developments in Pd-catalyzed oxygen-related organic reactions are summarized in alignment with each key factor. To close, we discuss the challenges and opportunities for photocatalysis research at this unique intersection as well as the potential impact on other research fields.

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Section: Integrating Metallic Pd With Other Metalsmentioning

confidence: 99%

“…[ 101 ] It is known that double bonds can be oxidized by O 2 in the present of Pd nanocrystals. [ 102 ] In this Pd/MOF system, the C=C double bond in cinnamyl alcohol was fully protected, making an important contribution to the selectivity of organic reactions. As discussed in Section 4.2.2, uniform MOF channels Adv.…”

Section: Progress Reportmentioning

confidence: 99%

Palladium‐Based Nanomaterials: A Platform to Produce Reactive Oxygen Species for Catalyzing Oxidation Reactions

et al. 2015

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“…Previous study via NMR spectroscopy revealed that the palladium-catalysed camphene deuteriation reaction involves intermediates r-vinylcamphene-palladium [31]. This fact in addition to commonly reactions promoted by palladium, allows suggesting a possible pathway of formation of aldehyde camphene [32]. This way, the b-hydride shift results in an unstable unsaturated vinylic alcohol, and this intermediate could then undergoes a tautomerization process resulting at the end into (1c) carbonylic product.…”

Section: Pdcl 2 -Catalysed Camphene Oxidation: a Brief Discussionmentioning

confidence: 93%

Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process

Oliveira

Silva

2009

Catal Lett

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Currently, the oxidative transformations of natural olefins are complicated for competitive reactions such as isomerization, skeletal rearrangements and nucleophilic addition. These concurrent reactions are promoted by metal reoxidant, normally a Lewis acid, and by protic solvent. In this article, the oxidation of terpenes, namely camphene, b-pinene, a-pinene and 3-carene were performed in PdCl 2 /H 2 O 2 /CH 3 CN system. This metal reoxidant-free system showed highly efficient, especially on camphene and b-pinene oxidation, which resulted in the selective conversion of these substrates into epoxy-derivates and allylic oxidation products, respectively. Additionally, the effects of the principal reactional parameters such as the peroxide/catalyst and substrate/catalyst molar ratio were also investigated.

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“…Hydrogen peroxide is another frequently used terminal oxidant for epoxidations, and its use with manganese [384] and palladium [385] catalysts has been the subject of recent reviews. Garcia-Bosch and coworkers have demonstrated that metal-catalyzed disproportionation of hydrogen peroxide in some catalytic systems can be suppressed by using a large excess of acetic acid as an additive, presumably facilitating the formation of peracetic acid [386].…”

Section: Using Other Oxidants Without Metal Catalystsmentioning

confidence: 99%

“…For example, higher yields and ees are obtained with the (R,S)-complex (384) for the epoxidation of indene (387, Scheme 2.61). However, N-toluenesulfonyl-1,2,3,4-tetrahydropyridine (389) gave better results using the (R,R)-diastereomer (385). An analysis of the transition-state enthalpy and entropy terms indicates that the selectivity in the former reaction is enthalpy driven, while the latter result reflects a combination of enthalpy and entropy factors [430].…”

Section: (S)-313mentioning

confidence: 99%

Three‐Membered Heterocycles. Structure and Reactivity

Murphree

2011

Modern Heterocyclic Chemistry

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Pd-mediated epoxidation of olefins

Cited by 37 publications

References 100 publications

Palladium‐Based Nanomaterials: A Platform to Produce Reactive Oxygen Species for Catalyzing Oxidation Reactions

Palladium‐Based Nanomaterials: A Platform to Produce Reactive Oxygen Species for Catalyzing Oxidation Reactions

Palladium-Catalysed Oxidation of Bicycle Monoterpenes by Hydrogen Peroxide in Acetonitrile Solutions: A Metal Reoxidant-Free and Environmentally Benign Oxidative Process

Three‐Membered Heterocycles. Structure and Reactivity

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