ChemInform Abstract: Decarboxylative Coupling Reactions

Gooßen, Lukas J.; Goossen, Käthe

doi:10.1002/chin.201341259

Cited by 14 publications

(18 citation statements)

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“…Modern TM-catalyzed decarboxylation methodologies were developed under the impulsion of Goossen's group as a part of the Pd/Cu-catalyzed decarboxylative cross-coupling reactions. [27][28][29][30] Limited to the strict protodecarboxylation methodologies, these studies focused particularly on the copper-catalyzed transformation of substituted benzoic acids, [31][32][33] and only a few examples related to cinnamic derivatives were reported. Goossen's group initially described a Cucatalyzed efficient procedure for the protodecarboxylation of various benzoic acids (i.e.…”

Section: Introductionmentioning

confidence: 99%

Preparation of functional styrenes from biosourced carboxylic acids by copper catalyzed decarboxylation in PEG

et al. 2014

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A general protocol for the copper-catalyzed decarboxylation of α,β-unsaturated carboxylic acids in PEG, particularly of biosourced cinnamic acid analogues, is reported. Moderate to high isolated yields (31-96%) towards the styrene derivatives were obtained. For the first time, decarboxylation of α-amino acids to the corresponding amines was successfully performed with good to high yields and extended to the decarboxylation of a few condensed heterocyclic compounds. Both the use of PEG as a green solvent and direct separation of the pure product of the reaction by distillation permitted the reuse of the solvent and the Cu-based catalytic system over several cycles without deactivation. This was extended to the synthesis of 4-vinylguaiacol on the laboratory scale in an average 92% yield. † Electronic supplementary information (ESI) available. See

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Section: Introductionmentioning

confidence: 99%

Preparation of functional styrenes from biosourced carboxylic acids by copper catalyzed decarboxylation in PEG

et al. 2014

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“…I am convinced that it has meanwhile become the rule rather than the exception for the discovery of a chemical reaction to result from an intentional invention process with a clearly defined target". 3 It is not surprising that metal-catalyzed reactions depend on the nature and architecture of ligands surrounding the central ion (for a theoretical description of metal-ligand bonds, see a recent review 4 ). Oxidation reactions catalyzed by nanoparticles in which neighboring metal atoms play the role of surrounding ligands have become especially popular.…”

Section: Introductionmentioning

confidence: 99%

C–H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity

Shul'pin

2013

Dalton Trans.

165

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This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2 fragment. This provokes the O-O bond rupture in the hydrogen peroxide molecule as is assumed for the role of Fe(2+) ions in the Fenton system.

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“…Decarboxylation reactions of metal carboxylates, RCO 2 M, to yield organometallics, RM, continue to attract considerable interest in synthetic applications as inexpensive and environmentally benign sources of R for incorporation into organic molecules. With appropriate metals and substrates, these reactions can be made catalytic.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Decarboxylative Coupling of Allyl Acetate: Role of the Metal Centers in the Organometallic Cluster Cations [CH₃Cu₂]⁺, [CH₃AgCu]⁺, and [CH₃Ag₂]⁺

et al. 2013

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Metal-catalyzed decarboxylative coupling reactions offer new opportunities for formation of C−C bonds. Here, multistage ion trap mass spectrometry experiments together with DFT calculations are used to examine the role of the metal centers in coinage metal cluster catalyzed decarboxylative coupling of allyl acetate in the gas phase via a simple two-step catalytic cycle. In step 1, the metal acetate cluster cation [CH 3 CO 2 Cu 2 ] + , [CH 3 CO 2 AgCu] + , or [CH 3 CO 2 Ag 2 ] + is subjected to collision-induced dissociation to yield the organometallic cluster cation [CH 3 Cu 2 ] + , [CH 3 AgCu] + , or [CH 3 Ag 2 ] + , respectively.Step 2 involves subjecting these organometallic cluster cations to ion−molecule reactions with allyl acetate with the aim of generating 1-butene and re-forming the metal acetate cluster cations to close the catalytic cycle. Experiment and theory reveal the role of the two metal centers in both steps of the gas-phase catalytic reaction. All three metal acetates undergo decarboxylation (step 1), although when competing reactions are taken into account, the yield of [CH 3 Cu 2 ] + is highest (83.3%). Ion−molecule reactions of the organometallic cations with allyl acetate all proceed at the collision rate; however, the types of products formed and their yields vary considerably. For example, only [CH 3 Cu 2 ] + and [CH 3 AgCu] + undergo the C−C bond-coupling reaction (step 2) in yields of 52.7% and 1.2%, respectively. Overall the dicopper clusters are the superior decarboxylative coupling catalysts, since they give the highest yields of the desired products for both steps 1 and 2. These results highlight that the reactivity of organometallic coinage metal clusters can be "tuned" by varying the composition of the metal core.

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ChemInform Abstract: Decarboxylative Coupling Reactions

Abstract: Review: 124 refs.

Cited by 14 publications

References 1 publication

Preparation of functional styrenes from biosourced carboxylic acids by copper catalyzed decarboxylation in PEG

Preparation of functional styrenes from biosourced carboxylic acids by copper catalyzed decarboxylation in PEG

C–H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity

Catalytic Decarboxylative Coupling of Allyl Acetate: Role of the Metal Centers in the Organometallic Cluster Cations [CH₃Cu₂]⁺, [CH₃AgCu]⁺, and [CH₃Ag₂]⁺

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ChemInform Abstract: Decarboxylative Coupling Reactions

Abstract: Review: 124 refs.

Cited by 14 publications

References 1 publication

Preparation of functional styrenes from biosourced carboxylic acids by copper catalyzed decarboxylation in PEG

Preparation of functional styrenes from biosourced carboxylic acids by copper catalyzed decarboxylation in PEG

C–H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity

Catalytic Decarboxylative Coupling of Allyl Acetate: Role of the Metal Centers in the Organometallic Cluster Cations [CH3Cu2]+, [CH3AgCu]+, and [CH3Ag2]+

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Catalytic Decarboxylative Coupling of Allyl Acetate: Role of the Metal Centers in the Organometallic Cluster Cations [CH₃Cu₂]⁺, [CH₃AgCu]⁺, and [CH₃Ag₂]⁺