Catalytic Hydrogenation of Amides to Amines under Mild Conditions

Stein, Mario; Breit, Bernhard

doi:10.1002/ange.201207803

Cited by 31 publications

(13 citation statements)

References 36 publications

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Section: Angewandte Chemiementioning

confidence: 99%

“…[14-16, 18, 19] In sharp contrast to reported heterogeneous catalysts,P t/V/HAP enabled the highly chemoselective hydrogenation of various aromatic amides without arene hydrogenation to afford the corresponding amines in excellent yields (entries [16][17][18][19][20][21][22]. [19] To elucidate the reasons for the high activity of Pt/V/HAP, we characterized Pt/V/HAP using electron microscopy and X-ray absorption fine structure (XAFS) analysis.Arepresentative secondary-electron image of Pt/V/HAP after treatment with H 2 under our reaction conditions (30 bar H 2 , 70 8 8C) shows the formation of Pt nanoparticles of am ean diameter of 2.2 nm on the HAP surface (Figure 1a). [24] Furthermore,t he mild reaction conditions (30 bar H 2 ,R T) also allowed selective amide hydrogenation with ahalogen group remaining intact (entries 17).…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[6] Thea chievement of hydrogenation of amides under mild reaction conditions, ideally lower than 30 bar H 2 and 70 8 8C, [6] is listed as aleading candidate in 12 key innovative research areas for the future sustainable production of pharmaceuticals. [11][12][13][14][15][16] Recently,o ther Re-based multi-metallic catalytic systems such as Pt/Re/In, [17] Pt/Re/ TiO 2 , [18] and Pd/Re/carbon [19] have enabled the use of lower H 2 pressures (5-70 bar) and temperatures (120-160 8 8C). In 1988, Dobson reported ac atalyst with much improved efficiency, namely abimetallic Pd/Re catalyst enabled amide hydrogenation at 130 bar H 2 and 200 8 8C.…”

mentioning

confidence: 99%

“…[12] Fuchikami et al and Whyman et al also developed bimetallic catalysts consisting of Ru/Re,R u/Mo,R h/Re,a nd Rh/Mo, which facilitated hydrogenation under milder reaction conditions (Ru/Re:5 0-100 bar H 2 ,1 50-160 8 8C; Ru/Mo:2 0-100 bar H 2 ,1 30-160 8 8C). [11][12][13][14][15][16] Recently,o ther Re-based multi-metallic catalytic systems such as Pt/Re/In, [17] Pt/Re/ TiO 2 , [18] and Pd/Re/carbon [19] have enabled the use of lower H 2 pressures (5-70 bar) and temperatures (120-160 8 8C). An alternative approach, using homogeneous ruthenium-based catalysts at 10-80 bar H 2 and 80-220 8 8C, has important practical drawbacks such as difficulty of catalyst reuse,t he need for synthetically complex ligands,a nd low selectivities arising from unavoidable by-production of alcohols through C À Nb ond cleavage with decreasing reaction temperature.…”

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confidence: 99%

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Mild Hydrogenation of Amides to Amines over a Platinum‐Vanadium Bimetallic Catalyst

et al. 2017

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Hydrogenation of amides to amines is an important reaction, but the need for high temperatures and H pressures is a problem. Catalysts that are effective under mild reaction conditions, that is, lower than 30 bar H and 70 °C, have not yet been reported. Here, the mild hydrogenation of amides was achieved for the first time by using a Pt-V bimetallic catalyst. Amide hydrogenation, at either 1 bar H at 70 °C or 5 bar H at room temperature was achieved using the bimetallic catalyst. The mild reaction conditions enable highly selective hydrogenation of various amides to the corresponding amines, while inhibiting arene hydrogenation. Catalyst characterization showed that the origin of the catalytic activity for the bimetallic catalyst is the oxophilic V-decorated Pt nanoparticles, which are 2 nm in diameter.

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Section: Angewandte Chemiementioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Mild Hydrogenation of Amides to Amines over a Platinum‐Vanadium Bimetallic Catalyst

et al. 2017

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“…Im ersten Fall entstehen große Mengen an Abfall, die bisher bekannten Hydrierungen erfordern drastische Bedingungen von über 200 °C und einem H2‐Druck bis zu 990 bar, die mit vielen funktionellen Gruppen nicht kompatibel sind. Breit und Mitarbeiter zeigten, dass mit auf Graphit geträgerten bimetallischen Pd/Re‐Katalysatoren die Reduktion unter moderaten Bedingungen gelingt 86. Auch tertiäre Amine sind so zugänglich, unter den Reaktionsbedingungen werden Phenylringe zu Cyclohexanen hydriert.…”

Section: Grund‐ Und Feinchemikalienunclassified

Chemical Exchange Saturation Transfer (CEST) Agents: Quantum Chemistry and MRI

Feng

Zhu

et al. 2015

Chemistry A European J

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Diamagnetic chemical exchange saturation transfer (CEST) contrast agents offer an alternative to Gd3+-based contrast agents for MRI. They are characterized by containing protons that can rapidly exchange with water and it is advantageous to have these protons resonate in a spectral window that is far removed from water. Here, we report the first results of DFT calculations of the 1H nuclear magnetic shieldings in 41 CEST agents, finding that the experimental shifts can be well predicted (R2 = 0.882). We tested a subset of compounds with the best MRI properties for toxicity and for activity as uncouplers, then obtained mice kidney CEST MRI images for three of the most promising leads finding 16 (2,4-dihydroxybenzoic acid) to be one of the most promising CEST MRI contrast agents to date. Overall, the results are of interest since they show that 1H NMR shifts for CEST agents—charged species—can be well predicted, and that several leads have low toxicity and yield good in vivo MR images.

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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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Catalytic Hydrogenation of Amides to Amines under Mild Conditions

Cited by 31 publications

References 36 publications

Mild Hydrogenation of Amides to Amines over a Platinum‐Vanadium Bimetallic Catalyst

Mild Hydrogenation of Amides to Amines over a Platinum‐Vanadium Bimetallic Catalyst

Chemical Exchange Saturation Transfer (CEST) Agents: Quantum Chemistry and MRI

Introduction to Pyrrolidone and Caprolactam Chemistry

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