Ruthenium‐Catalyzed Reductive Amidation without an External Hydrogen Source

Yagafarov, Niyaz Z.; Muratov, Karim; Biriukov, Klim O.; Usanov, Dmitry L.; Chusova, Olga; Perekalin, Dmitry S.; Chusov, Denis

doi:10.1002/ejoc.201701527

Cited by 10 publications

(4 citation statements)

References 59 publications

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“…The key advantage of this reducing agent is the lack of external hydrogen source, which leads to unique selectivity often surpassing more traditional, hydride‐based reducing agents . Previously, we developed a method for reductive amidation with carbon monoxide as the reducing agent using homogeneous rhodium and ruthenium catalysts . We decided to develop a method of reductive amidation using heterogeneous catalysis which might be more suitable for potential industrial application of this method.…”

Section: Catalysts Screeningmentioning

confidence: 99%

Reductive Amidation without an External Hydrogen Source Using Rhodium on Carbon Matrix as a Catalyst

et al. 2019

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An efficient method for preparation of secondary amides from primary amides and aldehydes using rhodium on carbon matrix as catalyst was developed. The method does not require any external hydrogen source and carbon monoxide is used as a reducing agent. The most active rhodium catalysts were characterized by BET, TEM and XPS techniques. Unexpectedly, it was found that heterogeneous rhodium on carbon matrix works as precatalyst for homogenous active species due to leaching of rhodium to the solution. Various secondary amides were synthesized and checked for antifungal activity. 4‐Methoxy‐N‐(4‐methoxybenzyl)benzamide demonstrated promising activity against Rhizoctonia Solani.

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Section: Catalysts Screeningmentioning

confidence: 99%

Reductive Amidation without an External Hydrogen Source Using Rhodium on Carbon Matrix as a Catalyst

et al. 2019

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“…The first reaction is known as a key reaction for contemporary green chemistry, requiring solutions for minimization of waste production [65]. Several high efficient catalytic systems (on base of Ru [66e68] or Rh [69]) were suggested for the amides formation from alcohols and amines [66,67] or via reductive amidation of aldehydes without an external hydrogen source [68,69]. Recently, an alternative approach, an oxidative amidation of alcohols, was developed.…”

Section: Introductionmentioning

confidence: 99%

Hexacoppergermsesquioxanes as complexes with N-ligands: Synthesis, structure and catalytic properties

Kulakova

Korlyukov

Zubavichus

et al. 2019

Journal of Organometallic Chemistry

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A simple and versatile strategy of synthesis of cage metallagermaniumsesquioxanes is demonstrated for isolation of Cu 6-based phenylgermsesquioxanes 1e6. Structure of newly synthesized coppergermsesquioxanes was established by single-crystal X-ray diffraction analysis. General principle of these cages' topology implies the presence of two linear Cu 3 fragments, coordinated by three pairs of ligands. These are: (i) cyclic germsesquioxanes [PhGeO 1,5 ] 5 , products 1e6, (ii) 1,10-phenanthrolines, (1, 3e5) or 2,2'bipyridines, (2, 6), (or and (iii) OX species (X ¼ H, 1e2, CH 3 , 3, H and C 2 H 5 O, 4, HCO, 5, CH 3 CO, 6). Appearance of non-expected species (formiate for 5, acetate for 6), resulted from corresponding alcohols used as reaction media, points at easyness of oxidation processes in the conditions of such selfassembling reactions. Catalytic tests showed high activity of complexes 1 and 2 as precatalysts in homogeneous oxidations of alkanes (cyclohexane, methylcyclohexane, n-heptane, cis-1,2dimethylcyclohexane with hydrogen peroxide in acetonitrile solution. Hydroxyl radicals take part in the reaction. The same complexes catalyze oxidation of alcohols (cyclohexanol, 2-heptanol, 1phenylethanol) to corresponding ketones with tert-butyl hydroperoxide in almost 100% yield. With the addition of various alkyl ammonium salts, complex 2 could also furnish corresponding amides in high yield.

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“…Furthermore, from a sustainability point of view, it is highly desirable to develop new methodologies that are capable of utilizing industrial byproducts as components of chemical synthesis. In this regard, we have been interested in the synthetic use of the deoxygenative potential of carbon monoxide, a multimillion-ton byproduct of several major industrial processes (e.g., steel making) . Herein, we report expansion of this paradigm to a new type of chemistry, namely, atom- and step-economical synthesis of esters from aldehydes or ketones and carboxylic acids.…”

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confidence: 99%

Atom- and Step-Economical Ruthenium-Catalyzed Synthesis of Esters from Aldehydes or Ketones and Carboxylic Acids

et al. 2018

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We developed a ruthenium-catalyzed reductive ester synthesis from aldehydes or ketones and carboxylic acids using carbon monoxide as a deoxygenative agent. Multiple factors influencing the outcome of the reaction were investigated. Best results were obtained for commercially available and inexpensive benzene ruthenium chloride; as low as 0.5 mol % of the catalyst is sufficient for efficient reaction. Competitive studies demonstrated that the presence of even 1000 equiv of alcohol in the reaction mixture does not lead to the corresponding ester, which clearly indicates that the process is not a simple reductive esterification but a novel type of Ru-catalyzed redox process.

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Ruthenium‐Catalyzed Reductive Amidation without an External Hydrogen Source

Cited by 10 publications

References 59 publications

Reductive Amidation without an External Hydrogen Source Using Rhodium on Carbon Matrix as a Catalyst

Reductive Amidation without an External Hydrogen Source Using Rhodium on Carbon Matrix as a Catalyst

Hexacoppergermsesquioxanes as complexes with N-ligands: Synthesis, structure and catalytic properties

Atom- and Step-Economical Ruthenium-Catalyzed Synthesis of Esters from Aldehydes or Ketones and Carboxylic Acids

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