Oxidative Carbonylation Of Alkynes Research Articles

Oxidative carbonylation of alkynes in self-oscillating mode. Effect of the nature of substrates on the dynamic behavior of reaction system

The oxidative carbonylation of alkynes in the oscillation mode was studied. The influence of the nature of substrates, alkynes and alcohols, on the pattern of oscillations was considered. The role of oxidants, I2 and H2O2, in this process was demonstrated. The reaction network of the process was formulated, and four hypothetical mechanisms were selected.

Palladium(II, I, 0) Complexes in Catalytic Reactions of Oxidative Carbonylation

The mechanisms of carbonylation of alkenes, alkynes, and alcohols, including the mechanism of oxidative carbonylation of alkynes in the regime of self-oscillations catalyzed by Pd(II), Pd(I), or Pd(0) complexes, are analyzed. It is shown that the main reasons for the appearance of self-oscillations in the oxidation reactions are nonlinear and autocatalytic steps of generation and termination of active centers. The results of studying the functions of para-benzoquinone as an oxidant, ligand, and catalyst in the oxidative reactions are generalized. It is found that Pd(0) complexes with para-benzoquinone can catalyze oxidation reactions.

ChemInform Abstract: Synthesis and Structure of New Triphenylphosphine π‐Complexes of Palladium(0) with p‐Benzoquinone and Their Role in the Oxidative Carbonylation of Alkynes.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis and structure of new triphenylphosphine π-complexes of palladium(0) with p-benzoquinone and their role in the oxidative carbonylation of alkynes

The complexes Pd(η2-Q)(PPh3)22H2Q and Pd2(μ-η2,η2-Q)2(PPh3)2 (where Q and H2Q are p-benzoquinone and hydroquinone, respectively) were synthesised and structurally characterised, and their catalytic activity in the oxidative carbonylation of phenylacetylene to methyl phenylpropiolate was examined.

Oxidative Carbonylation of Alkynes in an Oscillation Mode: I. Concentration Limits for Oscillations in the Course of Phenylacetylene Carbonylation and Possible Mechanisms of the Process

An oscillating reaction of alkyne oxidative carbonylation is studied in a PdI2–KI–CH3OH catalytic system. Concentration limits for oscillations are found. A tentative kinetic model for the process is proposed. The mechanism of oscillations is discussed.

ChemInform Abstract: Combined Oxidative and Reductive Carbonylation of Terminal Alkynes with Palladium Iodide‐Thiourea Catalysts.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Combined oxidative and reductive carbonylation of terminal alkynes with palladium iodide-thiourea catalysts

Oxidative carbonylation of alkynes can be carried out catalytically in the absence of added oxidants if it is coupled with a reductive carbonylation process at the expense of the same alkyne invilved in the oxidative process. Maleic esters (from oxidative carbonylation) and unsaturated lactones (from reductive carbonylation) are the main products formed under the catalytic action of palladium iodide complexes with thiourea (tu). A complex, formally corresponding to the ionic formula [PdI(tu) 3]I, allows the reaction of alkylacetylenes at room temperature and atmospheric pressure. With activated alkynes such as phenylacetylene, or with alkynes containing coordinating groups, other palladium complexes with two or four molecules of thiourea are also active, although to a lesser extent. Identification of the organic by-products gives a hint of the mechanism by which coupling of oxidative and reductive carbonylation occurs.

A New Catalytic Reaction: Oxidative Carbonylation of Alkynes to Alkynylcarboxylic Acid Esters

A new catalytic reaction – oxidative carbonylation of alkynes in the PdCl 2 CuCi system – and the reaction mechanism have been proposed based on the unusual effects of oxygen and copper(i) salts on this process and the key role of σ-alkynylcopper(i) complexes in the reaction.

σ-Alkynylcopper(i) and σ-alkynylpalladium(ii) complexes as intermediates in catalytic oxidative carbonylation of alkynes to alkynoates

Hypothetical mechanisms of oxidative carbonylation of alkynes to alkynoates in the PdCl2-CuCl2-base system are discusssed. σ-Alkynylcopper(i) and σ-alkynylpalladium(ii) complexes are considered to be the most probable intermediates in the process. A kinetic model of the reaction is proposed. The oxidative carbonylation of RC≡CCu in the PdCl2-CuCl2-base system leads to the formation of RC≡CCOOR'.