The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations

Keith, John A.; Henry, Patrick M.

doi:10.1002/anie.200902194

Cited by 283 publications

(178 citation statements)

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“…Numerous late transition metals, such as those based on gold, silver, copper, ruthenium, iron, palladium, and platinum, have been developed as catalysts for hydroalkoxylation. It is recognized that the well-studied palladiumcatalyzed Wacker oxidation proceeds by initial complexation of an olefin to the electrophilic palladium center followed by nucleophilic attack of an oxygen nucleophile, similar to the first step in hydroalkoxylation [111]. If β-hydride elimination is slowed relative to protonolysis of the metal-carbon bond, then saturated hydroalkoxylation products will be formed instead of Wacker oxidation products.…”

Section: Hydroalkoxylation Of Unsaturated C-c Bondsmentioning

confidence: 99%

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Julian

2013

Topics in Heterocyclic Chemistry

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The intramolecular hydrofunctionalization of carbon-carbon multiple bonds has emerged as a powerful way to form cyclic structures. A particularly important class of reactions involves the use of amine or alcohol nucleophiles, and alkenes or allenes as electrophiles, to form pyrrolidine, piperidine, tetrahydrofuran, and tetrahydropyran heterocycles in a highly efficient manner using late transition metal catalysts. Asymmetric methods for hydroamination and hydroalkoxylation reactions have recently emerged, allowing for the enantioselective synthesis of such saturated heterocycles. This review covers recent developments (over the last 5-10 years) in late transition metal-catalyzed hydroamination and hydroalkoxylation reactions that generate saturated heterocycles.

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Section: Hydroalkoxylation Of Unsaturated C-c Bondsmentioning

confidence: 99%

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Julian

2013

Topics in Heterocyclic Chemistry

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“…The mechanistic analyses in the laboratory have been mainly done by means of deuterium-labeling experiments and stereochemical studies. 25 The oxidation of C 2 H 4 carried out in D 2 O gives CH 3 CHO as the only product, 9 whereas the process using C 2 D 4 in H 2 O generates CD 3 CDO. 7 These results indicate that hydrogen transfers between carbon atoms take place intramolecularly (there is no exchange with protons from the solvent).…”

Section: Mechanistic Studies From Experimentsmentioning

confidence: 99%

“…Goddard and co-workers were the first to point out that β-hydride elimination from -OH groups is not accessible (energy barrier of 151.3 kJ/mol). 3 Instead, they 65 propose an alternative through a chloride-mediated reductive elimination where HCl and Pd(0) form directly. Later, EshtiaghHosseini et al published a quite similar mechanism with analogous conclusions for the H-transfer processes (Fig.…”

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Challenges in modelling homogeneous catalysis: new answers from ab initio molecular dynamics to the controversy over the Wacker process

et al. 2014

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We present here a review on the mechanistic studies of the Wacker process stressing the long controversy about the key reaction steps. We give an overview of the previous experimental and theoretical works on the topic. Then we describe the importance of the most recent Ab Initio Molecular Dynamics (AIMD) calculations in modelling organometallic reactivity in water. As a prototypical example of homogeneous catalytic reactions, the Wacker process poses serious challenges to modelling. The adequate description 10 of the multiple role of the water solvent is very difficult by using static quantum chemical approaches including cluster and continuum solvent models. In contrast, such reaction systems are suitable for AIMD, and by combining with rare event sampling techniques, the method provides reaction mechanisms and the corresponding free energy profiles. The review also highlights how AIMD has helped to obtain novel understanding of the mechanism and kinetics of the Wacker process.

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“…Originally dedicated to the binding situation of the complex anion of the Zeise salt [PtCl 3 (ethene)] -, it soon became clear that homogeneously metal-catalyzed transformations of olefins can be described and understood using this concept [4][5][6][7]. Probably the most prominent examples of such olefin complexes are the Pd derivatives of the Zeise anion [PdCl 3 (olefin)] − , which were the pivotal species of today's technically most important organocatalytic process, the Wacker Process (or Wacker Oxidation), which was developed starting in the 1950s [7][8][9][10].About 80 years after Roelen's hydroformylation, on a list of recently identified "holy grails" in chemistry "perfect catalysis" is prominently in the top ten [11] and homogeneous transition metal catalysis provides the basis for many desired transformations, e.g., in C-H aminations, in site-selective bond activations, for the functionalization of alkanes or in oxidative couplings yielding complex target molecules. Even since the rise of "metal-free" organo-catalysis at the beginning of our millennium and its enormous impact on organic transformations, the meanwhile established "classical" (transition) metal mediated applications reside as solid pillars in the toolbox for chemical synthesis [12][13][14].…”

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confidence: 99%

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confidence: 99%

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

2018

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Man-made homogeneous catalysis with the aid of transition metal compounds looks back on a long history of almost one hundred years. Still, more detailed insight into the underlying mechanisms is warranted. The knowledge of how transition metals with their specific/characteristic properties, such as oxidations states, redox chemistry, spin states, kinetics, and coordination preference will contribute to these processes paving the way to optimize existing processes, and to finding new exciting organic, inorganic, and organometallic transformations and to broaden the substrate scope through catalyst design. This special issue collects very recent mechanistic insight from experimental, theoretical, and mixed experimental-theoretical approaches.At the very end of the 19th century, Alfred Werner established the basis of our modern understanding of (transition) metal complexes [1]. When Otto Roelen discovered and developed the hydroformylation reaction (or Oxo Process) in the late 1930s, probably the first milestone in homogeneous catalysis, serendipity played an important role [2,3]. A deeper understanding of the specific interactions of ligands and metals came only later with the development of binding concepts such as the ligand field theory and the molecular orbital theory, e.g., the Dewar-Chatt-Duncanson model, which was developed in the 1950s for the binding of olefins to transition metals [4]. Originally dedicated to the binding situation of the complex anion of the Zeise salt [PtCl 3 (ethene)] -, it soon became clear that homogeneously metal-catalyzed transformations of olefins can be described and understood using this concept [4][5][6][7]. Probably the most prominent examples of such olefin complexes are the Pd derivatives of the Zeise anion [PdCl 3 (olefin)] − , which were the pivotal species of today's technically most important organocatalytic process, the Wacker Process (or Wacker Oxidation), which was developed starting in the 1950s [7][8][9][10].About 80 years after Roelen's hydroformylation, on a list of recently identified "holy grails" in chemistry "perfect catalysis" is prominently in the top ten [11] and homogeneous transition metal catalysis provides the basis for many desired transformations, e.g., in C-H aminations, in site-selective bond activations, for the functionalization of alkanes or in oxidative couplings yielding complex target molecules. Even since the rise of "metal-free" organo-catalysis at the beginning of our millennium and its enormous impact on organic transformations, the meanwhile established "classical" (transition) metal mediated applications reside as solid pillars in the toolbox for chemical synthesis [12][13][14]. Recent Nobel Prizes in chemistry, i.e., 2010 to Richard F. Heck, Ei-ichi Negishi and Akira Suzuki, 2005 to Yves Chauvin, Robert H. Grubbs and Richard R. Schrock, as well as 2001 to William S. Knowles, Ryoji Noyori and K. Barry Sharpless [14,15] clearly highlight homogeneous transition metal catalysis as an outstanding discipline, crucial for various are...

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The Mechanism of the Wacker Reaction: A Tale of Two Hydroxypalladations

Cited by 283 publications

References 60 publications

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Synthesis of Saturated Heterocycles via Metal-Catalyzed Alkene Hydroamination or Hydroalkoxylation Reactions

Challenges in modelling homogeneous catalysis: new answers from ab initio molecular dynamics to the controversy over the Wacker process

From Mechanisms in Homogeneous Metal Catalysis to Applications in Chemical Synthesis

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