Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Language: Английский

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Cycloheptyl-fused-PNN-manganese catalyzed asymmetric transfer hydrogenation of ketones

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 564, P. 114274 - 114274

Published: June 8, 2024

Language: Английский

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Efficient Cu-ZnO/TiO₂ Catalyst for Direct N-Methylation of N-Methylaniline with CO₂ and H₂

ACS Sustainable Chemistry & Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

The preparation of methyl-substituted amines by direct N-methylation with CO2/H2 is an important reaction for CO2 utilization and organic synthesis. However, the design construction effective stable non-noble-metal catalysts this remain challenging. Here, a cheap non-noble-Cu-based catalyst was prepared applied in N-methylaniline H2. 5%Cu-ZnO(3.75%)/TiO2 showed 98.8% yield initial TOF 7.7 h–1 after 24 h under 453 K, 1.5 MPa CO2, 4.5 H2, which superior to 5%Cu/TiO2, 5%Cu/ZnO, reported Cu-based catalysts. Furthermore, can be reused at least four times various excellent selectivity. characterizations experimental results that Cu0 active site, exhibited largest surface amount, thereby contributing catalytic performance. mechanism H2 proposed based on spectroscopic studies, kinetic control experiments. proceeded HCHO N-methylformanilide intermediates, formation from rate-determining step.

Language: Английский

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Enhancing enantioselectivity of manganese catalyst for asymmetric transfer hydrogenation of ketones through P,N,N-chelation of a cyclooctyl pyridine

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 437, P. 115682 - 115682

Published: July 31, 2024

Language: Английский

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Chemoselective Hydrogenolysis of Urethanes to Formamides and Alcohols in the Presence of More Electrophilic Carbonyl Compounds

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25562 - 25568

Published: Aug. 8, 2024

The development of methods for the chemical recycling polyurethanes is recognized as an urgent issue. Herein, we report Ir-catalyzed hydrogenolysis urethane C–O bond to produce formamides and alcohols, where both ester amide functionalities are tolerated. chemoselectivity observed counterintuitive generally accepted electrophilicity order carbonyl compounds. Hydrogenolysis urea isocyanurate, potential byproducts in polycondensation process polyurethanes, also achieved alongside selective degradation themselves, which affords diformamides diols. time-course hydrogenative polyurethane reveals that cleavage occurs not from terminal, but any part polymer chain. present catalysis offers a novel method polyurethane-containing waste.

Language: Английский

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Hydrogenolysis of Urethanes and Ureas Catalyzed by Manganese Complex Supported by Bidentate PN Ligand

Organometallics, Journal Year: 2024, Volume and Issue: 43(9), P. 924 - 928

Published: April 18, 2024

Hydrogenolysis of less reactive carbonyl compounds such as urethanes and ureas is a challenging but promising transformation to utilize new chemical feedstocks, plastic waste carbon dioxide fixation products. In these transformations, pincer-type complexes consisting Ru Mn have been intensively investigated catalyst design with bidentate ligand systems has rarely explored. We report here the synthesis complex supported by PN phosphino pyrrolido coordination sites, molecular structure which fully characterized. The catalyzed hydrogenolysis ureas. case 1,3-diphenylurea, formanilide was obtained product. addition, present did not promote hydrogenation carboxamides, showing unique reactivity that preferentially reduces over in contrast general order compounds.

Language: Английский

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Indazole enhances Ru-catalyzed hydrogenation of unsaturated bonds

Organic Chemistry Frontiers, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A practical approach is presented for the highly selective hydrogenation of various unsaturated compounds using a cutting-edge Ru/PNN catalytic system, resulting in high turnover numbers and substantial production valuable pharmaceuticals.

Language: Английский

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Catalytic materials based on metals (ions) used in the upcycling of plastics and polymers into fuels and valuable chemicals as part of sustainable development

Materials Science and Engineering R Reports, Journal Year: 2024, Volume and Issue: 162, P. 100881 - 100881

Published: Nov. 23, 2024

Language: Английский

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Noninnocent Spectator Ligands Facilitate CO Ligand-Stabilized Mn(I) Metal-Catalyzed Hydrogenation of Urea Derivatives or Carbamates to the More Reactive Formamides

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4911 - 4920

Published: March 7, 2025

Language: Английский

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Manganese PNN pincer complex for hydrogenation of carbamate and urea derivatives: Reaction mechanism examined by DFT calculations

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 556, P. 113923 - 113923

Published: Feb. 14, 2024

A comprehensive computational study is reported here on the mechanism of reaction through which a Mn(I) pincer catalyst able to assist hydrogenation process carbamate and urea derivatives, chosen as representative linker units polyurethanes. Four substrate models, have been examined in order evaluate their influence polyurethanes generate useful alcohols amines organic building blocks. The outcomes exploration highlight different behavior assisting or carbamide derivatives steps whole mechanism. Indeed, for first step, viability ligand-assisted has found only involves reversible structural change ligand that can partially detach from metal favor coordination molecule be processed. instead, go formation an intermediate interacts with complex without binding. second common all cases requires exploitation hemilabile nature PNN ligand. From calculated energies put into play it clearly appears great ability catalyzing both derivatives.

Language: Английский

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