Multi‐Dentate Phosphine Ligand Derived from Cyclotetrasiloxane and Its Application in Palladium‐Catalyzed Alkoxycarbonylation of Alkenes DOI
Mengli Liu, Xuening Fei,

Chuanzhi Xu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(11)

Published: July 19, 2024

Abstract The development of phosphine ligands continues to be essential for palladium‐catalyzed homogeneous carbonylation reactions, particularly in achieving high regioselectivity. In this study, a cyclosiloxane‐based multi‐dentate ligand, L1 (V4‐4Ph 2 P), characterized by its thermal stability and oxidation resistance, was synthesized through the radical addition secondary phosphines double bonds tetravinyltetramethylcyclotetrasiloxane. then used Pd‐catalyzed alkoxycarbonylation variety olefins, including terminal internal alkenes, cyclic aromatic alkenes as well tetra‐, tri‐ 1,1‐disubstituted afford desired esters with moderate good yields. As elucidated via DFT calculations situ IR spectroscopy, optimum spatial chelation modes Pd−H active species were responsible enhancement catalytic efficiency.

Language: Английский

Highly efficient palladium-catalyzed carbonylation reactions of terpenes. DOI
Abdelouahd Oukhrib, Philippe Kalck, Martine Urrutigoı̈ty

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 531, P. 216453 - 216453

Published: Feb. 12, 2025

Language: Английский

Citations

0
Palladium-Catalyzed Cascade Carbonylation Reaction To Construct Ester Derivatives DOI
Ming Li,

Shan-Mei Xu,

Fei Yang

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 24, 2025

We have developed a palladium-catalyzed ester carbonylation reaction that enables the synthesis of ester-substituted benzofuran derivatives in single step through introduction alkyl halides undergoing situ hydrolysis and alkynyl aryl iodides. This method demonstrates broad applicability to both primary secondary while maintaining excellent functional group compatibility under low palladium loading conditions. Notably, this strategy significantly expands scope reactions.

Language: Английский

Citations

0
DFT Investigation of the Mechanism of Methoxycarbonylation of Styrene by Palladium Chloride DOI Open Access
Shanti G. Patra, Anjan K. Saha, Pratim Kumar Chattaraj

et al.

Published: Oct. 21, 2024

The alkoxycarbonylation of styrene by palladium chloride is studied employing the density functional theory (DFT). Initially, [PdCl3]– reacts with methanol to form methoxy-bound intermediate, which undergoes β-hydride elimination key intermediate [PdCl2H]–. Then, a 1,2-insertion reaction takes place linear and branched alkyl coordinated PdII. Then CO coordination followed 1,1-insertion leads formation acyl intermediate. Next, methanolysis esters. Previous reports other catalysts suggested intermolecular/intramolecular transition state (TS) high activation barrier, this step was bottleneck. To best our knowledge, it first time we have considered two-step mechanism for alcoholysis ester mechanism. After metal, oxidative addition PdIV square pyramidal reductive regeneration metal hydride active Deeper insight into nature bonding at TSs are obtained through energy decomposition natural orbital chemical valence (EDA-NOCV) quantum atoms in molecules (QTAIM).

Language: Английский

Citations

1
DFT Investigation of the Mechanism of Methoxycarbonylation of Styrene by Palladium Chloride DOI Creative Commons
Shanti G. Patra,

Aritra Saha,

Pratim Kumar Chattaraj

et al.

Chemistry, Journal Year: 2024, Volume and Issue: 6(6), P. 1593 - 1607

Published: Dec. 5, 2024

The alkoxycarbonylation of styrene by palladium chloride is studied employing the density functional theory (DFT). Initially, [PdCl3]– reacts with methanol to form methoxy-bound intermediate, which undergoes β-hydride elimination key intermediate [PdCl2H]–. Then, a 1,2-insertion reaction takes place linear and branched alkyl coordinated PdII. CO coordination followed 1,1-insertion leads formation acyl intermediate. Next, methanolysis esters. Previous reports other catalysts suggested intermolecular/intramolecular transition state (TS) high activation barrier, this step was bottleneck. To best our knowledge, first time we have considered two-step mechanism for alcoholysis ester mechanism. After metal, oxidative addition PdIV square pyramidal reductive regeneration metal hydride active Deeper insight into nature bonding at TSs obtained through energy decomposition natural orbital chemical valence (EDA-NOCV) quantum atoms in molecules (QTAIM).

Language: Английский

Citations

1
Multi‐Dentate Phosphine Ligand Derived from Cyclotetrasiloxane and Its Application in Palladium‐Catalyzed Alkoxycarbonylation of Alkenes DOI
Mengli Liu, Xuening Fei,

Chuanzhi Xu

et al.

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(11)

Published: July 19, 2024

Abstract The development of phosphine ligands continues to be essential for palladium‐catalyzed homogeneous carbonylation reactions, particularly in achieving high regioselectivity. In this study, a cyclosiloxane‐based multi‐dentate ligand, L1 (V4‐4Ph 2 P), characterized by its thermal stability and oxidation resistance, was synthesized through the radical addition secondary phosphines double bonds tetravinyltetramethylcyclotetrasiloxane. then used Pd‐catalyzed alkoxycarbonylation variety olefins, including terminal internal alkenes, cyclic aromatic alkenes as well tetra‐, tri‐ 1,1‐disubstituted afford desired esters with moderate good yields. As elucidated via DFT calculations situ IR spectroscopy, optimum spatial chelation modes Pd−H active species were responsible enhancement catalytic efficiency.

Language: Английский

Citations

0