The metal-promoted dehydrogenation of cyclic thioethers S(C(5)H(9))(R) (R = C(5)H(9), Ph) to give the corresponding cycloalkenes, S(C(5)H(7))(R), using the [Rh{Ph(2)P(CH(2))(3)PPh(2)}](+) fragment is reported.
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http://dx.doi.org/10.1039/c1dt10503e | DOI Listing |
J Org Chem
January 2025
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati 517619, India.
The development of efficient and robust catalytic systems based on earth-abundant transition metals for fundamentally new transformations is crucial for sustainable chemical synthesis. Herein, an effective and selective Ni-catalyzed dehydrogenative coupling of alcohols with hydrazines with the liberation of ammonia gas is reported. Although several methods were documented for the -alkylation reaction, the present strategy is conceptually novel, and the reaction proceeds through a pathway involving N-N bond cleavage of phenylhydrazine followed by hydrogen autotransfer.
View Article and Find Full Text PDFJ Org Chem
January 2025
Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, Jodhpur, Rajasthan 342037, India.
An Earth-abundant Mn-PNP pincer complex-catalyzed terpenylation of cyclic and acyclic ketones and secondary alcohol 1-phenylethanol using isoprenoid derivatives prenol, nerol, phytol, solanesol, and E-farnesol as allyl surrogates is reported. The C-C coupling reactions are green and atom-economic, proceeding via dehydrogenation of alcohols following a hydrogen autotransfer methodology aided by metal-ligand cooperation.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Applied Chemistry, National Yang Ming Chiao Tung University, 1001 University Road, Hsinchu 30010, Taiwan.
This study presents a method for synthesizing functionalized hydrodibenzofuran derivatives. Using palladium catalysis, -aryl cyclic vinylogous esters undergo dehydrogenative intramolecular arylation at the vinylic carbon. Preliminary kinetic isotope effect studies suggest that the C(aryl)-H bond cleavage may be the rate-determining step.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Institut für Organische Chemie, Justus-Liebig-Universität Gießen, Heinrich-Buff-Ring 17, 35392 Gießen, Germany.
We report the synthesis, isolation, and characterization of a stable donor-acceptor substituted -quinodimethane (QDM). This system with an imidazolidine scaffold as the donor can also be referred to as acceptor-substituted --heterocyclic quinodimethane (NHQ). We have examined the extent of polarization of the conjugated π-system using single-crystal X-ray diffraction, NMR and UV/vis spectroscopy, cyclic voltammetry, and DFT computations.
View Article and Find Full Text PDFJ Am Chem Soc
November 2024
Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, United States.
The interaction between interfacial water and transition metal oxides is a primary enabling step for the oxygen evolution reaction (OER). RuO is a prototypical OER electrocatalyst whose ability to activate interfacial water molecules is essential to its OER activity. We image the dissociation of surface water into OH* and O* on RuO(110), where * denotes adsorbed species, using atomic force microscopy.
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