Evidence for the Intermediacy of (η
            <sup>3</sup>
            ‐Allyl)palladium Complexes in the Palladium‐Catalyzed Acryloxylation of Cycloalkenes: Unexpected Oxidation of 1,5‐Cyclooctadiene

Jabre-Truffert, Sylvaine; Delmas, Anne-Marie; Grennberg, Helena; Waegell, B.

doi:10.1002/(sici)1099-0690(200001)2000:1<219::aid-ejoc219>3.0.co;2-#

Cited by 5 publications

(2 citation statements)

References 16 publications

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“…Reactions for substituted cycloalkenes and linear alkenes afforded good yields with several isomeric acetates. This catalytic system also worked efficiently for the acyloxylation of alkenes and cycloalkenes. , …”

Section: Oxidative C−x Bond Formations Between Two Nucleophilesmentioning

confidence: 99%

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

Liu,

Zhang,

Shi

et al. 2011

Chem. Rev.

1,788

363

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Section: Oxidative C−x Bond Formations Between Two Nucleophilesmentioning

confidence: 99%

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

Liu,

Zhang,

Shi

et al. 2011

Chem. Rev.

1,788

363

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“…In particular, five-, six-, seven-, and eight-membered cycloolefins are oxidized to the corresponding allylic carboxylates (Scheme ) . This catalytic system is also effective for the acyloxylation of alkenes and cycloalkenes 96 …”

Section: 22 Intermolecular Reactionsmentioning

confidence: 99%

C−C, C−O, C−N Bond Formation on sp² Carbon by Pd(II)-Catalyzed Reactions Involving Oxidant Agents

et al. 2007

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Palladium‐Catalyzed Aerobic Intermolecular Cyclization of Acrylic Acid with 1‐Octene to Afford α‐Methylene‐γ‐butyrolactones: The Remarkable Effect of Continuous Water Removal from the Reaction Mixture and Analysis of the Reaction by Kinetic, ESI‐MS, and XAFS Measurements

Miyoshi¹,

Akatsuka²,

Okuoka³

et al. 2012

Chemistry A European J

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Further study of our aerobic intermolecular cyclization of acrylic acid with 1-octene to afford α-methylene-γ-butyrolactones, catalyzed by the Pd(OCOCF(3))(2)/Cu(OAc)(2)⋅H(2)O system, has clarified that the accumulation of water generated from oxygen during the reaction causes deactivation of the Cu cocatalyst. This prevents regeneration of the active Pd catalyst and, thus, has a harmful influence on the progress of the cyclization. As a result, both the substrate conversion and product yield are efficiently improved by continuous removal of water from the reaction mixture. Detailed analysis of the kinetic and spectroscopic measurements performed under the condition of continuous water removal demonstrates that the cyclization proceeds in four steps: 1) equilibrium coordination of 1-octene to the Pd acrylate species, 2) Markovnikov-type acryloxy palladation of 1-octene (1,2-addition), 3) intramolecular carbopalladation, and 4) β-hydride elimination. Byproduct 2-acryloxy-1-octene is formed by β-hydride elimination after step 2). These cyclization steps fit the Michaelis-Menten equation well and β-hydride elimination is considered to be a rate-limiting step in the formation of the products. Spectroscopic data agree sufficiently with the existence of the intermediates bearing acrylate (Pd-O bond), η(3)-C(8)H(15) (Pd-C bond), or C(11)H(19)O(2) (Pd-C bond) moieties on the Pd center as the resting-state compounds. Furthermore, not only Cu(II), but also Cu(I), species are observed during the reaction time of 2-8 h when the reaction proceeds efficiently. This result suggests that the Cu(II) species is partially reduced to the Cu(I) species when the active Pd catalytic species are regenerated.

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Evidence for the Intermediacy of (η ³ ‐Allyl)palladium Complexes in the Palladium‐Catalyzed Acryloxylation of Cycloalkenes: Unexpected Oxidation of 1,5‐Cyclooctadiene

Cited by 5 publications

References 16 publications

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

C−C, C−O, C−N Bond Formation on sp² Carbon by Pd(II)-Catalyzed Reactions Involving Oxidant Agents

Palladium‐Catalyzed Aerobic Intermolecular Cyclization of Acrylic Acid with 1‐Octene to Afford α‐Methylene‐γ‐butyrolactones: The Remarkable Effect of Continuous Water Removal from the Reaction Mixture and Analysis of the Reaction by Kinetic, ESI‐MS, and XAFS Measurements

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Evidence for the Intermediacy of (η 3 ‐Allyl)palladium Complexes in the Palladium‐Catalyzed Acryloxylation of Cycloalkenes: Unexpected Oxidation of 1,5‐Cyclooctadiene

Cited by 5 publications

References 16 publications

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

Bond Formations between Two Nucleophiles: Transition Metal Catalyzed Oxidative Cross-Coupling Reactions

C−C, C−O, C−N Bond Formation on sp2 Carbon by Pd(II)-Catalyzed Reactions Involving Oxidant Agents

Palladium‐Catalyzed Aerobic Intermolecular Cyclization of Acrylic Acid with 1‐Octene to Afford α‐Methylene‐γ‐butyrolactones: The Remarkable Effect of Continuous Water Removal from the Reaction Mixture and Analysis of the Reaction by Kinetic, ESI‐MS, and XAFS Measurements

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Product

Resources

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Evidence for the Intermediacy of (η ³ ‐Allyl)palladium Complexes in the Palladium‐Catalyzed Acryloxylation of Cycloalkenes: Unexpected Oxidation of 1,5‐Cyclooctadiene

C−C, C−O, C−N Bond Formation on sp² Carbon by Pd(II)-Catalyzed Reactions Involving Oxidant Agents