Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
Silyl palladium cations (RP)Pd-SiR catalyze the ring opening, C-C bond forming, and functionalization of 5- and 6-membered cyclic allyl ethers with -silyl nucleophiles. Conditions for high regio-control are achieved by adjustments in the phosphine electronics, with the identity of the 2-substituent also influencing the functionalization location in unsymmetrical furans. Allyl alcohols are obtained with a regio-preference for terminal addition with unsubstituted ethers with -products being obtained with XantPhos and - with (4-CF-Ar) ligation. Styrenes dominate with phenyl-substituted dihydrofurans, and for 2-alkyl-substituted, secondary alcohols result from an allyl migration pathway. Mechanistic studies demonstrate the feasibility of Pd-Si bonds to facilitate C-O activation to yield π-allyl intermediates, and for one substrate class to also sequence π-allyl migration prior to nucleophilic addition. DFT calculations demonstrated the viability of silylium-activated ether as a competent ligand for Pd(0).
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.5c12528 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Engineering Brønsted Acidic Microenvironments via Strong Metal-Support Interaction in Single-Atom Pd/CeO for Acid-Free Acetalization Catalysis.
Inorg Chem
September 2025
College of Chemistry and Materials Science, The key Laboratory of Functional Molecular Solids, Ministry of Education, The Key Laboratory of Electrochemical Clean Energy of Anhui Higher Education Institutes, Anhui Provincial Engineering Laboratory for New-Energy Vehicle Battery Energy-Storage Materia
Conventional acid-catalyzed acetalization faces significant challenges in catalyst recovery and poses environmental concerns. Herein, we develop a CeO-supported Pd single-atom catalyst (Pd/CeO) that eliminates the reliance on liquid acids by creating a localized H-rich microenvironment through heterolytic H activation. X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses confirm the atomic dispersion of Pd via Pd-O-Ce coordination, while density functional theory (DFT) calculations reveal strong metal-support interactions (SMSI) that facilitate electron transfer from CeO oxygen to Pd, downshifting the Pd d-band center and optimizing H activation.
View Article and Find Full Text PDFFenton-Type and Poulos-Kraut Dual Mechanisms of HO Activation over Peroxidase-Mimicking Nanozymes Identified by Measurements.
Nano Lett
September 2025
State Key Laboratory of Chemo and Biosensing, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. China.
Current strategies for developing peroxidase-mimicking nanozymes seldom address the interplay between Fenton-type hemolytic and Poulos-Kraut heterolytic mechanisms in HO activation. To reveal the active centers, reaction intermediates, and dynamic structural transformations during catalysis, we investigated Fe-doped TiO (Fe-TiO) nanozymes that exhibit a dual-mechanism pathway. ambient-pressure electron spin resonance spectroscopy and Raman measurements revealed that HO molecules adsorb onto Fe-TiO surfaces, occupying oxygen vacancy sites (Ti-O-Ti) and forming peroxy bonds with Ti atoms (Ti-OOH).
View Article and Find Full Text PDFLewis-Brønsted Dual Acid Sites in WO Catalysts Facilitate Direct Photocatalytic Hydrodeoxygenation of Hydroxy Groups in Alcohols.
Angew Chem Int Ed Engl
August 2025
State Key Laboratory of Fine Chemicals, School of Chemistry, Dalian University of Technology, Dalian, Liaoning, 116024, China.
Efficient hydrodeoxygenation (HDO) of the hydroxy groups (C─OH) in alcohol molecules has attracted substantial attention due to its importance in many research fields such as organic synthesis and biomass conversion. Photocatalytic C─OH direct HDO is a promising but challenging process because of the difficulty in C─O bond activation due to the higher bond energy and strong polarity. A polarity enhancement strategy is proposed and a WO catalyst possessing Lewis-Brønsted dual acid sites is developed to realize the direct HDO of alcohols under ambient conditions.
View Article and Find Full Text PDFHeterolytic Cleavage of LPd-SiR Bonds Enable the Ring-Opening C-C Functionalization of Nonstrained Ethers.
J Am Chem Soc
August 2025
Caudill Laboratories, Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, United States.
Silyl palladium cations (RP)Pd-SiR catalyze the ring opening, C-C bond forming, and functionalization of 5- and 6-membered cyclic allyl ethers with -silyl nucleophiles. Conditions for high regio-control are achieved by adjustments in the phosphine electronics, with the identity of the 2-substituent also influencing the functionalization location in unsymmetrical furans. Allyl alcohols are obtained with a regio-preference for terminal addition with unsubstituted ethers with -products being obtained with XantPhos and - with (4-CF-Ar) ligation.
View Article and Find Full Text PDFRepurposing haemoproteins for asymmetric metal-catalysed H atom transfer.
Nature
August 2025
Department of Chemistry, University of Basel, Basel, Switzerland.
Transition metal-hydrides have been widely exploited in catalysis for the hydrofunctionalization of unsaturated moieties, including carbonyls, alkenes and alkynes. To complement heterolytic metal-hydride bond cleavage, metal-hydride hydrogen atom transfer (MHAT) has recently gained attention, as a promising strategy for radical hydrofunctionalization of unactivated alkenes, thus enabling late-stage diversification of complex molecules. However, owing to the weak interactions between the prochiral organic radical and the enantiopure catalyst, asymmetric MHAT remains challenging.
View Article and Find Full Text PDF