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http://dx.doi.org/10.1002/chem.201103973 | DOI Listing |
One-pot tandem dehydrogenative cross-coupling of primary and secondary alcohols was catalyzed by three ruthenium complexes [1-()-4--(furan-2-ylmethyl)acetamido-1,2,4-triazol-5-ylidene]Ru(-cymene)Cl [R = Et (1b), i-Pr (2b), Bn (3b)], of amido-functionalized 1,2,4-triazole derived N-heterocyclic carbene (NHC) ligands. Density Functional Theory (DFT) calculations were employed for the ruthenium (1b) precatalyst to understand this reaction mechanism completely, and the mechanisms adapted are divided categorically into three steps (i) nucleophilic substitution of chloride ions by alcohols, (ii) dehydrogenation of primary and secondary alcohols, and (iii) olefin and ketone hydrogenation. Our mechanistic study reveals that the formation of a deprotonated Ru-alcoholate (A) or (E) intermediate is favorable compared to the protonated form (A') or (E') from (1b) by associative nucleophilic substitution.
View Article and Find Full Text PDFOrg Biomol Chem
January 2019
Research Center of Green Pharmaceutical Technology and Process, Hubei Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang 443002, China.
A chemoselective 1,2-reduction of cycloalkyl vinyl ketones via asymmetric transfer hydrogenation is described. The reduction proceeded smoothly with a chiral diamine ruthenium complex as a catalyst and a HCOOH-NEt3 azeotrope as both a hydrogen source and solvent under mild conditions. A wide range of 1-cycloalkyl chiral allylic alcohols were obtained in good yields and up to 87% ee.
View Article and Find Full Text PDFChemistry
May 2012
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland.
Chem Commun (Camb)
May 2011
Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans, 16, E-43007 Tarragona, Spain.
The concept of metal-ligand bifunctionality can be employed for an efficient activation of N-H bonds by well-defined ruthenium amido complexes. An enantioselective catalytic aza-Michael reaction was developed on the basis of this process, which gives rise to indoline β-amino acids.
View Article and Find Full Text PDFJ Organomet Chem
January 2011
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881, U.S.A.
The group's recent advances in catalytic carbon-to-heteroatom bond forming reactions of alkenes and alkynes are described. For the C-O bond formation reaction, a well-defined bifunctional ruthenium-amido catalyst has been successfully employed for the conjugate addition of alcohols to acrylic compounds. The ruthenium-hydride complex (PCy(3))(2)(CO)RuHCl was found to be a highly effective catalyst for the regioselective alkyne-to-carboxylic acid coupling reaction in yielding synthetically useful enol ester products.
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