4.8 Review

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

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Article Chemistry, Applied

Hydrogenation of Esters by Manganese Catalysts

Xiao-Gen Li et al.

Summary: The hydrogenation of esters catalyzed by a manganese complex of phosphine-aminopyridine ligand was developed. A variety of esters, including biomass-derived esters and lactones, can be efficiently hydrogenated to primary alcohols with yields of 63-98%. The manganese catalyst showed high activity for the hydrogenation of methyl benzoate, with turnover numbers (TON) as high as 45,000. Investigation of catalyst intermediates revealed that the amido manganese complex is the active species for the reaction.

ADVANCED SYNTHESIS & CATALYSIS (2022)

Article Chemistry, Physical

Manganese-Catalyzed Hydrogenation of Sclareolide to Ambradiol

Viktoriia Zubar et al.

Summary: The hydrogenation of (+)-Sclareolide to (-)-ambradiol catalyzed by a manganese pincer complex was achieved with high yield. The catalyst is easy to prepare, and the reaction conditions are relatively mild, with reproducible experimental results.

CHEMCATCHEM (2022)

Article Chemistry, Multidisciplinary

Manganese(i)-catalyzed access to 1,2-bisphosphine ligands

Luo Ge et al.

Summary: Chiral bisphosphine ligands play a key role in transition-metal-catalyzed asymmetric synthesis. However, the commonly used transition metals are expensive and scarce, and the synthesis of chiral phosphine ligands is complex. In this study, a catalytic asymmetric hydrophosphination reaction using a chiral complex of earth-abundant manganese(i) was developed. This reaction provides a short and efficient synthetic route to access easily obtainable and structurally tunable chiral bisphosphines, which can be used in asymmetric catalysis with earth-abundant metal-based organometallic catalysts.

CHEMICAL SCIENCE (2022)

Article Chemistry, Physical

E-Selective Manganese-Catalyzed Semihydrogenation of Alkynes with H2 Directly Employed or In Situ-Generated

Ronald A. Farrar-Tobar et al.

Summary: This study describes the selective semihydrogenation of alkynes using a Mn(I) alkyl catalyst, leading to good to excellent yields of E-alkenes. Mechanistic investigations reveal that the initially formed Z-isomer undergoes fast isomerization to the thermodynamically more stable E-isomer.

ACS CATALYSIS (2022)

Article Chemistry, Multidisciplinary

Evaluation of Manganese Catalysts for the Hydrogenative Deconstruction of Commercial and End-of-Life Polyurethane Samples

Laurynas Gausas et al.

Summary: Polyurethane (PU) is a commonly used thermoset plastic with complex structure, leading to challenges in recycling. The study shows that catalytic hydrogenation of PU materials using a manganese catalyst can effectively deconstruct PU into original monomer components for efficient recovery.

CHEMSUSCHEM (2022)

Article Chemistry, Multidisciplinary

Hydrogenative Depolymerization of Polyurethanes Catalyzed by a Manganese Pincer Complex

Viktoriia Zubar et al.

Summary: This report discusses the promising method of utilizing plastic waste through chemical recycling, specifically hydrogenative depolymerization using a Mn pincer complex catalyst. The key to success lies in the combination of the catalyst with elevated temperatures and appropriate solvents to ensure sufficient solubility of the polymers. The process successfully depolymerizes a wide range of polyurethane samples, releasing polyetherols and diaminotoluene in high yields.

CHEMSUSCHEM (2022)

Article Chemistry, Physical

Manganese-Catalyzed Reformation of Vicinal Glycols toα-HydroxyCarboxylic Acids with the Liberation of Hydrogen Gas

Satyadeep Waiba et al.

Summary: In this study, a sustainable catalytic pathway was developed to convert readily available feedstocks into valuable α-hydroxycarboxylic acid molecules. A bench stable metal complex was used as the catalyst, enabling the selective transformation of vicinal glycols into α-hydroxycarboxylic acids at low temperature. The protocol showed high efficiency and applicability for various types of vicinal glycols, with significant potential in the synthesis of bioactive molecules and biodegradable polymers.

ACS CATALYSIS (2022)

Article Chemistry, Multidisciplinary

Manganese catalyzed asymmetric transfer hydrogenation of ketones

Guang-Ya Zhang et al.

Summary: The study investigated the asymmetric transfer hydrogenation of a wide range of ketones catalyzed by manganese complex and chiral PxNy-type ligand under mild conditions. By using 2-propanol as a hydrogen source and combining [MnBr(CO)(5)] with chiral, 22-membered macrocyclic ligand (R,R,R',R')-CyP2N4 (L5) with 2% catalyst loading, various ketones could be enantioselectively hydrogenated to afford highly valuable chiral alcohols with up to 95% ee.

CHINESE CHEMICAL LETTERS (2021)

Review Chemistry, Applied

Recent Trends and Prospects in Homogeneous Manganese-Catalysed Epoxidation

Rose Mary Philip et al.

Summary: Epoxidation of alkenes is an important reaction in organic chemistry with significant potential in producing biochemically relevant compounds. Recent studies have focused on catalytic epoxidation using homogeneous manganese catalysts, particularly with porphyrin, Schiff base, Salen, and other ligands, showing advantages in green chemistry. The use of greener approaches, such as photo-catalysis, has been highlighted in recent reports, aiming to provide researchers with a better understanding of the reaction and catalyst selection.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Article Chemistry, Applied

Selective Construction of C-C and C=C Bonds by Manganese Catalyzed Coupling of Alcohols with Phosphorus Ylides

Xin Liu et al.

Summary: The manganese catalyzed coupling of alcohols with phosphorus ylides was found to be controllable in terms of selectivity for forming carbon-carbon single and double bonds by adjusting ligands and reaction conditions. Compared to previous methods using precious metal complexes, this system utilizes earth abundant manganese catalysts, allowing for C-C and C=C bond formation in a sequential one-pot reaction. Mechanistic studies revealed that C-C bonds were generated through a borrowing hydrogen pathway, while C=C bond formation followed an acceptorless dehydrogenative coupling pathway.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Article Chemistry, Multidisciplinary

Manganese-Catalyzed Asymmetric Hydrogenation of Quinolines Enabled by π-π Interaction

Chenguang Liu et al.

Summary: The article reports on the non-noble metal-catalyzed asymmetric hydrogenation of N-heteroaromatics, quinolines. A new chiral pincer manganese catalyst showed outstanding catalytic activity in the reaction, producing high yields and enantioselectivities. The precise regulation of enantioselectivity was ensured by a pi-pi interaction, achieving competitive turnover numbers with noble metal catalysts.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Physical

Four-Coordinated Manganese(II) Disilyl Complexes for the Hydrosilylation of Aldehydes and Ketones with 1,1,3,3-Tetramethyldisiloxane

Kyoka Saito et al.

Summary: The article discusses a method of catalytic hydrosilylation using manganese complexes, with improved catalytic efficiency achieved by modifying the structure of the complex and combining it with isocyanide.

CHEMCATCHEM (2021)

Article Chemistry, Inorganic & Nuclear

Manganese-Catalyzed Hydroboration of Terminal Olefins and Metal-Dependent Selectivity in Internal Olefin Isomerization- Hydroboration

Subhash Garhwal et al.

Summary: The study reports a manganese complex that shows high selectivity for terminal alkenes in hydroboration reactions, in contrast to cobalt which exhibits different selectivity towards internal alkenes, leading to different reaction pathways and product structures.

INORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

Manganese Catalyzed Direct Amidation of Esters with Amines

Zhengqiang Fu et al.

Summary: The development of a new transition metal catalyzed amide forming reaction with a wide substrate scope and low catalyst loading represents a novel approach to overcome the limitations of traditional methods.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

N-Alkylation of Amines with Alcohols Catalyzed by Manganese(II) Chloride or Bromopentacarbonylmanganese(I)

Dongyue Wei et al.

Summary: A manganese-catalyzed N-alkylation reaction has been demonstrated, providing access to diverse secondary amines in moderate-to-high yields. The catalytic system is practical, scalable, and suitable for synthesizing heterocycles with potential activity against Alzheimer's disease.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Multidisciplinary

Manganese-catalysed divergent silylation of alkenes

Jie Dong et al.

Summary: This study presents a new method for manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, utilizing a ligand-tuned metalloradical reactivity strategy. The reaction is redox-neutral and atom-economical, with broad substrate scope and excellent functional group tolerance, suitable for various synthetic applications on a gram scale.

NATURE CHEMISTRY (2021)

Article Chemistry, Inorganic & Nuclear

Cationic PCP and PCN NHC Core Pincer-Type Mn(I) Complexes: From Synthesis to Catalysis

Ruqaya Buhaibeh et al.

Summary: The coordination chemistry of NHC core pincer-type PCP and PCN ligands with a Mn(I) center was studied, revealing that Mn(I) complexes with bidentate and tridentate ligands exhibit different catalytic activities based on ligand structure.

ORGANOMETALLICS (2021)

Article Multidisciplinary Sciences

Robust and efficient hydrogenation of carbonyl compounds catalysed by mixed donor Mn(I) pincer complexes

Wenjun Yang et al.

Summary: In this study, a highly efficient manganese pincer pre-catalyst was reported, displaying high TOF values (up to 41,000 h(-1)) and stability (TON up to 200,000) at loadings as low as 5-200 ppm. The crucial role of catalyst activation step for the catalytic performance and stability of the system was highlighted, with activation using hydride donor promoters significantly improving catalytic performance and eliminating induction times. Manganese-based hydrogenation catalysts are shown to be sensitive to high temperatures, but this pre-catalyst offers a promising alternative.

NATURE COMMUNICATIONS (2021)

Article Chemistry, Physical

Dehydrogenation of Formic Acid to CO2 and H2 by Manganese(I)-Complex: Theoretical Insights for Green and Sustainable Route

Tiziana Marino et al.

Summary: This study presents a detailed computational investigation on a recently synthesized Mn(I)-dependent complex, which shows good catalytic performance in the dehydrogenation of formic acid. The calculated results confirm the robustness of the complex and its ability to reproduce experimental data, potentially inspiring the design of new efficient catalysts for hydrogen production.

CATALYSTS (2021)

Review Chemistry, Multidisciplinary

Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions

Yujie Wang et al.

Summary: The development of novel and efficient earth-abundant metal catalysts, with manganese as a rising star in catalytic hydrogenation and dehydrogenation reactions, has made significant progress since 2016. This review provides a comprehensive overview of homogeneous Mn-catalyzed hydrogenation and dehydrogenation reactions, emphasizing mechanistic understanding and future development trends in this promising field.
Article Chemistry, Applied

Catalytic Formal Hydroamination of Allylic Alcohols Using Manganese PNP-Pincer Complexes

Leandro Duarte de Almeida et al.

Summary: Several manganese-PNP pincer catalysts were used in the formal hydroamination of allylic alcohols to selectively obtain gamma-amino alcohols in high yields under mild conditions.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Article Chemistry, Multidisciplinary

Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation

Juana M. Perez et al.

Summary: Chiral Mn(I) complexes have been shown to activate H-P bonds, providing a general method for the hydrophosphination of internal and terminal alpha,beta-unsaturated nitriles. Metal-ligand cooperation, a previously unconsidered strategy for catalytic H-P bond activation, plays a key role in the mechanistic action of the Mn(I)-based catalyst. Computational studies support a stepwise mechanism for the hydrophosphination reaction and offer insights into the origin of enantioselectivity.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Multidisciplinary

Manganese-Catalyzed Dehydrogenative Silylation of Alkenes Following Two Parallel Inner-Sphere Pathways

Stefan Weber et al.

Summary: A novel manganese(I)-catalyzed dehydrogenative silylation reaction was reported, using an alkyl bisphosphine manganese(I) complex as the most active precatalyst. The reaction efficiently converted a variety of aromatic and aliphatic alkenes to their corresponding products with high selectivity at room temperature. Insights into the mechanism were provided based on experimental data and DFT calculations, revealing two parallel reaction pathways.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

Article Chemistry, Inorganic & Nuclear

Manganese-Catalyzed C(α)-Alkylation of Oxindoles with Secondary Alcohols via Borrowing Hydrogen

Jagannath Rana et al.

Summary: The general and efficient C(alpha)-alkylation of oxindoles with unactivated secondary alcohols as alkylating agents catalyzed by a newly developed NNN-Mn(II) complex demonstrates the importance of the NH moiety in the complex and M-L cooperation during the catalytic transformation.

ORGANOMETALLICS (2021)

Article Chemistry, Physical

Phosphine-Free Manganese Catalyst Enables Selective Transfer Hydrogenation of Nitriles to Primary and Secondary Amines Using Ammonia-Borane

Koushik Sarkar et al.

Summary: Primary and secondary amines were synthesized via nitrile hydrogenation using a borrowing hydrogenation strategy catalyzed by phosphine-free manganese complexes. The method is chemodivergent, allowing control over the final product by adjusting catalyst structure and reaction polarity. The protocol operates without the need for externally added base or high-pressure dihydrogen gas, providing a practical and efficient route to a variety of amines.

ACS CATALYSIS (2021)

Article Chemistry, Applied

Manganese-Catalyzed Selective Hydrogenative Cross-Coupling of Nitriles and Amines to Form Secondary Imines

Xiao-Gen Li et al.

Summary: Manganese complexes with tridentate PNN ligands have been synthesized as catalysts for hydrogenative cross-coupling reaction of nitriles and amines to form secondary imines. This reaction yielded a variety of unsymmetrical secondary imines in good yields with excellent selectivity. Investigation of catalyst intermediates suggested that an amido manganese complex may be the active catalyst species for this reaction.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Article Chemistry, Multidisciplinary

Manganese-Catalyzed Hydroborations with Broad Scope

Pradip Ghosh et al.

Summary: The reductive transformations of easily available oxidized matter play a crucial role in synthetic manipulation and chemical valorization. The use of liquid reducing agents and simple setups in catalytic hydrofunctionalization adds to its practicality. Metal-catalyzed hydroborations offer a productive platform for reductive valorizations of stable C=X electrophiles, as demonstrated in this study with the pre-catalyst Mn(hmds)(2) for the reduction of various functional groups under mild conditions, including successful depolymerizations.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Physical

Hydrogenation of CO2 to Methanol with Mn-PNP-Pincer Complexes in the Presence of Lewis Acids: the Formate Resting State Unleashed

David A. Kuss et al.

Summary: Balancing the interaction between the acidic additive and the catalyst to remove the formate ligand can unleash the full catalytic potential in the hydrogenation of CO2 to methanol. This optimized process using MACHO-Ph and Ti((OPr)-Pr-i)(4) as the most active system allows for a liquid phase conversion of CO2/H-2 with high efficiency.

CHEMCATCHEM (2021)

Article Chemistry, Multidisciplinary

Hydroboration of Nitriles, Esters, and Carbonates Catalyzed by Simple Earth-Abundant Metal Triflate Salts

Ranjeesh Thenarukandiyil et al.

Summary: Earth-abundant metals have become increasingly important in homogeneous catalysis, particularly in the hydroboration reactions of challenging substrates like nitriles, carbonates, and esters. The use of manganese(II) triflate salt in combination with potassium tert-butoxide and pinacolborane enables efficient hydroboration of these substrates with near quantitative yields in less than three hours at room temperature, showcasing a simple and effective methodology for these transformations. Further studies indicate that other earth-abundant metal triflate salts can also facilitate this reaction, expanding the scope of this catalytic process.

CHEMISTRY-AN ASIAN JOURNAL (2021)

Article Chemistry, Inorganic & Nuclear

Carbon Dioxide Hydrogenation to Formate Catalyzed by a Bench-Stable, Non-Pincer-Type Mn(I) Alkylcarbonyl Complex

Sylwia Kostera et al.

Summary: The catalytic reduction of carbon dioxide using a non-precious-metal precatalyst is efficient and selective in forming formate under mild conditions. Mechanistic insight into the catalytic reaction is provided by means of density functional theory calculations.

ORGANOMETALLICS (2021)

Article Chemistry, Inorganic & Nuclear

Manganese-Catalyzed Hydrogenation of Ketones under Mild and Base-free Conditions

Stefan Weber et al.

Summary: This paper investigated several Mn(I) complexes as catalysts for the homogeneous hydrogenation of ketones. The most active precatalyst was identified, and the reaction was carried out under base-free conditions at room temperature. Temperature-dependent selectivity for different compounds was observed in the reduction process.

ORGANOMETALLICS (2021)

Article Chemistry, Multidisciplinary

Manganese-New prominent actor in transfer hydrogenation catalysis

Karim Azouzi et al.

Summary: This review comprehensively covers transfer hydrogenation processes catalyzed by manganese organometallic complexes, with a focus on reduction reactions of various substances and ligand design for Mn-catalyzed asymmetric transfer hydrogenation reactions.

CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY (2021)

Article Chemistry, Applied

Manganese Catalyzed Hydrogenation of Azo (N=N) Bonds to Amines

Uttam Kumar Das et al.

Summary: The first example of homogeneously catalyzed hydrogenation of the N=N bond of azo compounds has been reported using a complex of an earth-abundant-metal. The hydrogenation reaction is catalyzed by a manganese pincer complex, proceeds under mild conditions, and yields amines, which makes this methodology a sustainable alternative route for the conversion of azo compounds. A plausible mechanism involving metal-ligand cooperation and hydrazine intermediacy is proposed based on mechanistic studies.

ADVANCED SYNTHESIS & CATALYSIS (2021)

Article Chemistry, Multidisciplinary

Hydroboration of Terminal Alkenes and trans-1,2-Diboration of Terminal Alkynes Catalyzed by a Manganese(I) Alkyl Complex

Stefan Weber et al.

Summary: The Mn-catalyzed hydroboration of terminal alkenes and the 1,2-diboration of terminal alkynes with pinacolborane have been successfully achieved. The most active pre-catalyst is a bench-stable alkyl bisphosphine Mn-I complex. The catalytic process involves migratory insertion of a CO ligand into the Mn-alkyl bond to yield an acyl intermediate, which further undergoes B-H bond cleavage or C-H bond cleavage for alkenes and alkynes, respectively, forming active Mn-I boryl and acetylide catalysts.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Review Chemistry, Inorganic & Nuclear

Homogeneously catalyzed acceptorless dehydrogenation of alcohols: A progress report

Monica Trincado et al.

Summary: This paper reviews recent advances in homogeneously catalyzed acceptorless alcohol dehydrogenation, highlighting the importance of metal-ligand cooperativity in catalyzing the reaction and the potential positive impact of introducing multifunctional cooperative ligands.

COORDINATION CHEMISTRY REVIEWS (2021)

Article Chemistry, Inorganic & Nuclear

Deciphering the Mechanistic Details of Manganese-Catalyzed Formic Acid Dehydrogenation: Insights from DFT Calculations

Neethinathan Johnee Britto et al.

Summary: A comprehensive density functional theory investigation revealed the detailed mechanistic landscape of aqueous-phase formic acid dehydrogenation catalyzed by a pyridyl-imidazoline-based Mn(I) catalyst. The stepwise mechanism was found to be kinetically and thermodynamically favorable for the production of a Mn-formate intermediate. The beta-hydride elimination process was identified as the rate-determining step, confirming experimental observations.

INORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

Manganese(I) Catalyzed α-Alkenylation of Amides Using Alcohols with Liberation of Hydrogen and Water

Biplab Keshari Pandia et al.

Summary: The unprecedented manganese-catalyzed direct alpha-alkenylation of amides using alcohols was reported, providing alpha,beta-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies showed that the selective olefination is facilitated by metal-ligand cooperation, resulting in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.

JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Organic

Recent advances in homogeneous base-metal-catalyzed transfer hydrogenation reactions

Daler Baidilov et al.

Summary: Catalytic transfer hydrogenation has become an appealing alternative for direct hydrogenation reactions due to its simplicity and mild reaction conditions. Research is now focused on developing sustainable catalysts using abundant first-row transition metals, with many novel examples appearing in the literature in recent decades.

TETRAHEDRON (2021)

Article Chemistry, Organic

Homogeneous first-row transition metal catalyst for sustainable hydrogen production and organic transformation from methanol, formic acid, and bio-alcohols

Jagannath Rana et al.

Summary: Recent advances in homogeneous first-row transition-metal catalyzed for hydrogen production and important organic transformations focus on earth-abundant 3d base-metal complexes, showing promise for sustainable catalysis development.

TETRAHEDRON (2021)

Article Chemistry, Organic

Manganese catalyzed enantio- and regioselective hydrogenation of α, β-unsaturated ketones using an imidazole-based chiral PNN tridentate ligand

Ze Wang et al.

Summary: This study demonstrates an enantioselective 1,2-reduction of alpha,beta-unsaturated ketones using a chiral pincer Mn catalyst, leading to the synthesis of chiral allyl alcohols with high catalytic activity and enantioselectivity. The process also provides a novel synthesis route for key pharmaceutical intermediates of cannabidiol.

TETRAHEDRON LETTERS (2021)

Article Chemistry, Physical

Manganese-Catalyzed Anti-Markovnikov Hydroamination of Allyl Alcohols via Hydrogen-Borrowing Catalysis

Kuhali Das et al.

Summary: This article presents a method for selective formal anti-Markovnikov hydroamination of allyl alcohols, enabling the synthesis of valuable gamma-amino alcohol building blocks. Catalyzed by a phosphine-free Earth's abundant manganese(I) complex, a wide range of hydroamination reactions were successfully conducted with excellent functional group tolerance. The mechanistic studies highlighted the importance of metal-ligand bifunctionality and ligand backbone hemilability for the success of this catalysis.

ACS CATALYSIS (2021)

Article Chemistry, Physical

Mechanistic Study of Metal-Ligand Cooperativity in Mn(II)-Catalyzed Hydroborations: Hemilabile SNS Ligand Enables Metal Hydride-Free Reaction Pathway

Matthew R. Elsby et al.

Summary: The study describes the chemoselective hydroboration of carbonyls using the paramagnetic bis-amido Mn[(SNSMe)-N-Me](2) complex (1). It was found that the bifunctional amido bis(thioether) ligand L plays a crucial role in the success of the reaction, while also ruling out the possibility of side reactions.

ACS CATALYSIS (2021)

Article Chemistry, Physical

Amino Acid Derived Chiral Aminobenzimidazole Manganese Catalysts for Asymmetric Transfer Hydrogenation of Ketones

Lixian Wang et al.

Summary: A series of Mn(I) catalysts with chiral bidentate benzimidazoles derived from easily available amino acids have been developed for asymmetric transfer hydrogenation (ATH), showing high activity and enantioselectivity. These phosphine-free chiral Mn catalysts can efficiently convert bulky substrates into drug intermediate alcohols, with a possible mechanism and enantiocontrol model proposed based on experimental and DFT studies.

ACS CATALYSIS (2021)

Review Chemistry, Organic

Acceptorless Dehydrogenative Coupling Reactions by Manganese Pincer Complexes

Pinaki Nad et al.

Summary: Acceptorless dehydrogenative coupling reactions using manganese catalyst is a promising and sustainable method for constructing carbon-carbon and carbon-heteroatom bonds. The methodology is highly atom economical, producing water and hydrogen as byproducts, and provides a unique opportunity for constructing various synthons and biologically important motifs. Recent progress in this field has been made with manganese catalysis based on pincer ligands for various homogeneous transformations.

ASIAN JOURNAL OF ORGANIC CHEMISTRY (2021)

Article Chemistry, Multidisciplinary

Acceptorless Dehydrogenation of Methanol to Carbon Monoxide and Hydrogen using Molecular Catalysts

Akash Kaithal et al.

Summary: The acceptorless dehydrogenation of methanol to carbon monoxide and hydrogen using homogeneous molecular complexes, particularly those containing ruthenium and manganese with the MACHO ligand framework, showed promising catalytic activities. The metal complex was found to mediate the initial fast dehydrogenation of methanol to formaldehyde and methyl formate followed by subsequent slow decarbonylation, resulting in gas mixtures with varying CO/H2 ratios.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2021)

Article Chemistry, Multidisciplinary

Redox-active ligand based Mn(i)-catalyst for hydrosilylative ester reduction

Soumi Chakraborty et al.

Summary: A new Mn(i) catalyst with a redox-active ligand is reported for the efficient hydrosilylation of esters to alcohols, with mechanistic investigations showing a strong cooperation between the ligand and metal in initiating the reaction through a ligand-based single electron transfer (SET) process activating the Si-H bond.

CHEMICAL COMMUNICATIONS (2021)

Article Chemistry, Organic

Transfer hydrogenation of N-heteroarenes with 2-propanol and ethanol enabled by manganese catalysis

Yingjie Gong et al.

Summary: A convenient manganese-catalyzed transfer hydrogenation method using alcohols as hydrogen sources for N-heteroarenes was presented. The use of a specific manganese pincer complex allowed for good to excellent isolated yields, with even biomass-derived ethanol being a viable option for the process. Detailed DFT calculations supported an outer sphere hydrogenation mechanism with hydride transfer as the rate-determining step.

ORGANIC CHEMISTRY FRONTIERS (2021)

Article Chemistry, Multidisciplinary

Manganese catalyzed switchable C-alkylation/alkenylation of fluorenes and indene with alcohols

Avijit Mondal et al.

Summary: The study successfully demonstrated the selective C-alkylation and olefination of fluorene and indene with alcohols using manganese catalyst, providing insights into the potential use of earth-abundant, nontoxic transition metals in place of rare noble metals in catalysis.

CHEMICAL COMMUNICATIONS (2021)

Review Chemistry, Multidisciplinary

Advancements in multifunctional manganese complexes for catalytic hydrogen transfer reactions

Kuhali Das et al.

Summary: Catalytic hydrogen transfer reactions are essential for the production of diverse molecular scaffolds, with manganese emerging as a viable alternative due to its abundance and sustainability. Strategies such as metal-ligand bifunctionality and hemilability play crucial roles in achieving desired catalytic activity and selectivity. The use of multifunctional ligand-based manganese complexes in various organic transformations has been detailed, highlighting the importance of ligand design for successful HT reactions.

CHEMICAL COMMUNICATIONS (2021)

Article Chemistry, Physical

Synthesis of 1,3-diketones from esters via liberation of hydrogen

Guoying Zhang et al.

Summary: The study presents a method for catalytic dehydrogenative rearrangement of esters into 1,3-diketones, mediated by both a base-acid catalyst and a dehydrogenation catalyst based on manganese. This approach allows for the conversion of green or sustainable and inexpensive ester starting materials into highly attractive 1,3-diketones for organic synthesis, with hydrogen as the only by-product.

CHEM CATALYSIS (2021)

Article Chemistry, Multidisciplinary

Indirect reduction of CO2 and recycling of polymers by manganese-catalyzed transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes

Xin Liu et al.

Summary: A manganese pincer complex is reported as a versatile catalyst for the transfer hydrogenation of amides, carbamates, urea derivatives, and polyurethanes, leading to the corresponding alcohols, amines, and methanol. This method represents an approach to the indirect reduction of CO2 and shows the first examples of reduction of carbamates and urea derivatives as well as C-N bond cleavage in amides by transfer hydrogenation. The general applicability of this methodology is demonstrated by successful reduction of various compounds with good to excellent yields.

CHEMICAL SCIENCE (2021)

Article Chemistry, Multidisciplinary

Reduction of Carboxylic Acids to Alcohols via Manganese(I) Catalyzed Hydrosilylation

Emanuele Antico et al.

Summary: The study demonstrated the reduction of carboxylic acids to alcohols using [MnBr(CO)(5)] as the catalyst and PhSiH3 as the reducing agent under mild conditions. The reaction could be performed with low catalyst loading or using the lowest reported amount of silane, showing promise for green and sustainable synthetic strategies in industrial production.

JACS AU (2021)

Article Chemistry, Multidisciplinary

Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts

Akash Kaithal et al.

Summary: Alcohol-assisted hydrogenation of carbon monoxide to methanol was achieved using homogeneous molecular complexes. The best performance was observed with a molecular manganese complex, with a turnover number of 4023 and turnover frequency of 857 h(-1) under optimized conditions. The reaction proceeds via formate ester as the intermediate, resulting in high selectivity for methanol formation and no accumulation of formate ester.

JACS AU (2021)

Review Chemistry, Organic

Recent advances in sustainable synthesis of N-heterocycles following acceptorless dehydrogenative coupling protocol using alcohols

Milan Maji et al.

Summary: This review summarizes recent advances in the synthesis of heterocycles using the ADC approach, which involves transition metal-catalyzed acceptorless dehydrogenative coupling using alcohols as greener substrates. Homogeneous and heterogeneous catalysis are both discussed in this review, showcasing environmentally benign methodologies for producing N-heterocycles.

ORGANIC CHEMISTRY FRONTIERS (2021)

Article Chemistry, Multidisciplinary

Manganese catalyzed C-alkylation of methyl N-heteroarenes with primary alcohols

Akash Jana et al.

Summary: A new study reports the alkylation of nine different classes of methyl-substituted N-heteroarenes using an environmentally friendly catalyst. The compounds are synthesized with high yields and selectivities, with water as the sole byproduct.

CHEMICAL COMMUNICATIONS (2021)

Article Chemistry, Physical

Enantioselective direct, base-free hydrogenation of ketones by a manganese amido complex of a homochiral, unsymmetrical P-N-P′ ligand

Chris S. G. Seo et al.

Summary: The use of manganese in homogeneous hydrogenation catalysis has shown great promise in terms of enantioselectivity, activity, and tolerance for base-sensitive substrates. NMR structural analysis and computational analysis have provided insights into the reaction mechanism and the influence of reactant structure on product enantiomeric selectivity.

CATALYSIS SCIENCE & TECHNOLOGY (2021)

Article Chemistry, Multidisciplinary

Carbon monoxide and hydrogen (syngas) as a C1-building block for selective catalytic methylation

Akash Kaithal et al.

Summary: A catalytic reaction using syngas as feedstock for the selective beta-methylation of alcohols was developed, with carbon monoxide and hydrogen gas as key components. The complex molecular structure involving earth-abundant manganese enables the generation of formaldehyde from syngas. This new syngas conversion method provides a pathway for installing methyl branches at carbon centers and synthesizing biologically active compounds, fine chemicals, and advanced biofuels.

CHEMICAL SCIENCE (2021)

Article Chemistry, Multidisciplinary

Manganese(I)-Catalyzed β-Methylation of Alcohols using Methanol as C1 Source

Akash Kaithal et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Review Chemistry, Applied

Manganese-Catalysed Dehydrogenative Coupling - An Overview

K. R. Rohit et al.

ADVANCED SYNTHESIS & CATALYSIS (2020)

Article Chemistry, Multidisciplinary

Manganese-Catalyzed β-Methylation of Alcohols by Methanol

Martin Schlagbauer et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Article Chemistry, Multidisciplinary

Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]-Hydrogenase

Hui-Jie Pan et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

Review Chemistry, Physical

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Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron Compound and Lewis Acid Co-catalyst

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ACS CATALYSIS (2015)

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2009)

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ORGANIC LETTERS (2009)

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ACCOUNTS OF CHEMICAL RESEARCH (2008)

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TETRAHEDRON LETTERS (2008)

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TETRAHEDRON LETTERS (2008)

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PURE AND APPLIED CHEMISTRY (2006)

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ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2006)

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2004)

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Platinum group metals in catalysis: Fabrication of catalysts and catalyst precursors

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Kinetic study of the hydrosilylation of acetophenone by [Rh(cod)Cl]2/(R)-BINAP

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ORGANOMETALLICS (2002)

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