Lipidic cubic phases (LCPs) can reduce Pd salts to palladium nanoparticles (PdNPs) of ∼5 nm size in their confined water channels under mild conditions. The resulting PdNP-containing LCPs were used as nanoreactor scaffolds to catalyze Suzuki-Miyaura cross-coupling reactions in the aqueous channels of the mesophase. To turn on catalysis, PdNP-containing LCPs were activated by swelling the aqueous channels of the lipidic framework, thereby enabling diffusion of the water-soluble substrates to the catalysts. The mesophases play a threefold role: they act as reducing agents for Pd, as limiting templates for their growth, and as support. The system was characterized and investigated by small-angle X-ray scattering (SAXS), cryo-transmission electron microscopy, dynamic light scattering, and nuclear magnetic resonance. Bulk LCPs and three dispersed palladium/lipid hybrid nanoparticle types were applied in the catalysis. The latter-liposomes, hexosomes, and cubosomes-can be obtained by design through combination of lipids and additives. The Suzuki-Miyaura cross-coupling of 5-iodo-2'-deoxyuridine and phenylboronic acid was used as a model reaction to study these systems. Bulk Pd-LCPs deliver the Suzuki-Miyaura product in 24 h in conversions up to 98% at room temperature, whereas with palladium/lipid dispersions at 40 °C, 68% of the starting material was transformed to the product after 72 h.
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http://dx.doi.org/10.1021/acs.langmuir.8b02905 | DOI Listing |
Inorg Chem
January 2025
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, P. R. China.
As an indispensable member of the reticular material family, metal-carbon-based organometallic frameworks (OMFs) remain largely underexplored, and no chiral OMFs (COMFs) have been reported thus far. Herein, we first report the construction of COMFs from a Pd-isocyanide OMF via nucleophilic addition to the Pd-isocyanide moiety with optically pure amines. The obtained Pd-bis(acyclic diaminocarbene) (Pd-BADC)-derived chiral OMFs display excellent applicability and can be reusable chiral catalysts to highly promote asymmetric Strecker and Suzuki-Miyaura cross-coupling reactions in a heterogeneous way.
View Article and Find Full Text PDFMolecules
December 2024
Laboratoire de Chimie de Coordination, CNRS, Toulouse-INP, Université de Toulouse, 31000 Toulouse, France.
In recent years, there has been growing interest in the development of greener alternatives to traditional reagents used in carbon-carbon coupling reactions, particularly in response to environmental concerns. The commonly used aryl halides, despite being highly reactive in the Suzuki-Miyaura coupling (SMC), pose significant environmental risks. As a result, research has shifted towards exploring the use of phenols, which are widely accessible and environmentally benign.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
Department of Chemistry, CMS College Kottayam (Autonomous), Kottayam, Kerala, 686001, India.
The Suzuki-Miyaura Coupling (SMC) reaction is a powerful method for forming carbon-carbon bonds in organic synthesis. Recent advancements in SMC reactions have introduced first-row transition metal catalysts, with zinc garnering significant interest due to its cost-effective and eco-friendly nature. Despite progress in experimental protocols, the mechanistic details of zinc-catalyzed SMC reactions are limited.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Osaka University: Osaka Daigaku, Department of Applied Chemistry, JAPAN.
Although numerous transition-metal catalyzed cross-coupling reactions of alkenyl electrophiles with a sulfur(VI) leaving group, mainly alkenyl sulfones, have been developed, most rely heavily on highly nucleophilic Grignard reagents, and the use of organoboron reagents remains challenging. We report herein facile preparation and the following Pd-catalyzed Suzuki-Miyaura cross-coupling reaction of alkenyl sulfoximine, a monoaza analog of sulfone. The condensation of alkyl sulfoximine with aldehydes, developed in this study, makes alkenyl sulfoximines more readily available.
View Article and Find Full Text PDFBeilstein J Org Chem
December 2024
Department of Chemistry, Faculty of Science, Bilkent University, Ankara 06800, Türkiye.
Acenaphthylene-fused heteroarenes with a variety of five- and six-membered heterocycles such as thiophene, furan, benzofuran, pyrazole, pyridine and pyrimidine were synthesized via an efficient Pd-catalyzed reaction cascade in good to high yields (45-90%). This cascade involves an initial Suzuki-Miyaura cross-coupling reaction between 1,8-dihalonaphthalenes and heteroarylboronic acids or esters, followed by an intramolecular C-H arylation under the same conditions to yield the final heterocyclic fluoranthene analogues. The method was further employed to access polyoxygenated benzo[]fluoranthenes, which are all structurally relevant to benzo[]fluoranthene-based fungal natural products.
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