Ruthenium‐Pincer‐Catalyzed Hydrogenation of Lactams to Amino Alcohols

Chen, Jiangbo; Wang, Jiaquan; Tu, Tao

doi:10.1002/asia.201800759

Cited by 26 publications

(9 citation statements)

References 75 publications

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“…In the methanol cycle, the hydrogenation of hemiaminal to methanol is rather straightforward as also shown in the hydrogenation of carbamate and urea derivatives by Ru-MACHO and similar pincer complexes. 53,[124][125][126][127][128][129][130][131] Scheme 4 shows two key resting state complexes A and B. The formation of metal-formate complex A via metal-hydride transfer to CO 2 followed by rearrangement in II with a small energy barrier is thermodynamically favored due to both metaloxygen bonding and N-HÁ Á ÁO hydrogen bonding interactions.…”

Section: Metal/nh Bifunctional Molecular Catalystsmentioning

confidence: 99%

Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions

et al. 2021

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Section: Metal/nh Bifunctional Molecular Catalystsmentioning

confidence: 99%

Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions

et al. 2021

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“…Both complexes present a Ru-BH 4 moiety, being able to deliver the active catalyst at the reaction conditions. In 2018, Tu et al 46 showed that the commercially available [Ru-MACHO-BH] complex is an active catalyst for the synthesis of protected and unprotected amino alcohols by deaminative hydrogenation of lactams employing catalytic amounts of K 3 PO 4 ( Fig. 2B9).…”

Section: Development Of Homogeneous Catalystsmentioning

confidence: 99%

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

et al. 2020

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Catalytic hydrogenation of amides is of great interest for chemists working in organic synthesis, as the resulting amines are widely featured in natural products, drugs, agrochemicals, dyes, etc. Compared to traditional reduction of amides using (over)stoichiometric reductants, the direct hydrogenation of amides using molecular hydrogen represents a greener approach. Furthermore, amide hydrogenation is a highly versatile transformation, since not only higher amines (obtained by CO cleavage), but also lower amines and alcohols, or amino alcohols (obtained by C-N cleavage) can be selectively accessed by fine tuning of reaction conditions. This review describes the most recent advances in the area of amide hydrogenation using H 2 exclusively and molecularly defined homogeneous as well as nanostructured heterogeneous catalysts, with a special focus on catalyst development and synthetic applications. T he development of green and sustainable methods is a central focus of modern organic synthesis and its applications in various areas of the chemical industry. In this respect, many reduction reactions, traditionally employing stoichiometric amounts of metal hydrides with inherent low atom efficiency 1 , can be favorably replaced by catalytic hydrogenations. In fact, the combination of molecular hydrogen and catalysts does not only allow avoiding formation of waste products 2 , it also opens the door to clean transformations based on renewable energies as the conversion of solar or wind energy to "green" hydrogen is likely to be implemented in the coming years. Among the many reduction reactions known, amide hydrogenation can be encountered as one of the most desired considering the importance of the derived amines in several branches of chemical industry. In fact, since the start of the Green Chemistry Institute Pharmaceutical Roundtable in the United States in 2005, several projects aimed to the achievement of a practical amide hydrogenation methodology have been supported 3,4. The long-term interest of the pharmaceutical industry in this specific transformation is explained by the fact that it ideally affords structurally complex amines, present in many of the currently employed drugs. Furthermore, amines are also in bulk and fine chemicals used in the manufacture of plastics, textiles, surfactants, dyes, and many more 5. Amides play a central role in the chemistry of life, as they are the key elements to generate peptides and proteins from amino acid monomers. At the same time, they are present in artificial

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“…Finally, full reduction of pyrrolidones and caprolactams to the corresponding amino alcohols has been accomplished by catalytic hydrogenation (425)(426)(427) and by reduction with sodium borohydride (428)(429)(430)(431) and samarium iodide (432) (Scheme 23).…”

Section: Reduction Of Pyrrolidones and Caprolactamsmentioning

confidence: 99%

“…Scheme 23Hydrogenation and reduction of pyrrolidones and caprolactams to N-substituted amino alcohols(427,428).…”

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Introduction to Pyrrolidone and Caprolactam Chemistry

Chenault

2021

Handbook of Pyrrolidone and Caprolactam Based Materials

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Pyrrolidones and caprolactams are important structural components of solvents, surfactants, polymers, natural products, and pharmaceuticals. This chapter provides an introduction to the structure, conformation, physical properties and reactivity of pyrrolidones and caprolactams. It begins with an overview of the nomenclature of lactams since there are several systems of nomenclature in practice, plus common names and various syncretisms. Next, the structures of pyrrolidone and caprolactam are discussed, starting with the X-ray crystal structures of pyrrolidone, N-methylpyrrolidone (NMP) and caprolactam. The conformational flexibility and ring strain of the two ring systems are also covered.Physical properties, such as dipole moments, the enthalpies of formation, vaporization and fusion, boiling points and melting points, are described. An attempt is made to put the properties of pyrrolidones and caprolactams into context with those of other lactams, amides and even lactones and cyclic ketones. Brønsted and Lewis basicity, acidity, hydrogen bonding and solubility are covered.Finally, a brief description of the basic reactivity of pyrrolidones and caprolactams is given. Topics covered are N-, O-, and α-C-alkylation, hydrolysis, reactions with organometallics, reduction, oxidation, and ring-opening polymerization. The intent is to give a concise physical organic perspective on reactivity (and stability) more than an extended treatise on synthetic elaborations. Definition and Nomenclature of LactamsLactams are cyclic amides in which both the carbonyl carbon and nitrogen atom of the amide group are part of a ring. The name, lactam, is a portmanteau of lactone (cyclic ester) and amide.Nomenclature of lactams follows a variety of conventions (Figure 1 and Table 1). The International Union of Pure and Applied Chemistry (IUPAC) recommends naming lactams as heterocyclic pseudoketones (IUPAC method 1) or by substituting lactam for the

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Ruthenium‐Pincer‐Catalyzed Hydrogenation of Lactams to Amino Alcohols

Cited by 26 publications

References 75 publications

Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions

Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Introduction to Pyrrolidone and Caprolactam Chemistry

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Ruthenium‐Pincer‐Catalyzed Hydrogenation of Lactams to Amino Alcohols

Cited by 26 publications

References 75 publications

Homogeneous and heterogeneous catalysts for hydrogenation of CO2 to methanol under mild conditions

Homogeneous and heterogeneous catalysts for hydrogenation of CO2 to methanol under mild conditions

Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen

Introduction to Pyrrolidone and Caprolactam Chemistry

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Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions

Homogeneous and heterogeneous catalysts for hydrogenation of CO₂ to methanol under mild conditions