General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones

Schönauer, Timon; Thomä, Sabrina L. J.; Kaiser, Leah; Zobel, Mirijam; Kempe, Rhett

doi:10.1002/chem.202004755

Cited by 15 publications

(7 citation statements)

References 44 publications

(40 reference statements)

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“…Thereby, structure refinements became possible for a range of materials, spanning nanoparticles, lanthanide-based 1D polymeric chains (Grebenyuk et al, 2021), superionic conductors (Gautam et al, 2019) and catalyst materials (Scho ¨nauer et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

Quick and robust PDF data acquisition using a laboratory single-crystal X-ray diffractometer for study of polynuclear lanthanide complexes in solid form and in solution

Tsymbarenko¹,

Grebenyuk²,

Burlakova³

et al. 2022

J Appl Crystallogr

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Self-assembled polynuclear lanthanide hydroxo complexes are important objects in the reticular chemistry approach to the design of various functional materials. Revealing their structure in the solid state and understanding the molecular mechanism of self-assembly in solution require a universal and reliable structural method. Pair distribution function (PDF) analysis is a powerful technique which enables structural insight for a wide range of crystalline and amorphous materials on the nanoscale, but commonly measurements are performed at synchrotron X-ray sources or on specially designed laboratory diffractometers. In the present paper, a standard Bruker D8 QUEST single-crystal X-ray diffractometer equipped with a micro-focus Mo tube and CMOS Photon III detector was adapted to measure PDF data of high quality with Q max = 16.97 Å–1 for solid and liquid samples. An improved data collection strategy and the original data reduction software FormagiX enable calibration and azimuthal full-frame integration of 2D frames, delivering reliable PDFs up to 80 Å with instrumental parameters Q damp = 0.018 Å−1 and Q broad = 0.010 Å−1. The effectiveness of the developed approach was demonstrated with reference samples and real-case studies of tetranuclear lanthanide hydroxocarboxylates in solid form and in solution.

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Section: Introductionmentioning

confidence: 99%

Quick and robust PDF data acquisition using a laboratory single-crystal X-ray diffractometer for study of polynuclear lanthanide complexes in solid form and in solution

Tsymbarenko¹,

Grebenyuk²,

Burlakova³

et al. 2022

J Appl Crystallogr

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“…To overcome the above-mentioned issues, significant advances have been recently made using precisely synthesized metal nanoparticle catalysts. For example, Beller’s group reported Co nanoparticles coated with a N-doped carbon layer through the pyrolysis of metal–nitrogen complexes, which serve as a kind of catalysts for nitrile hydrogenation with air stability and reusability. − This “N-doping strategy” is applicable to other air-stable metal catalysts for various types of hydrogenations. − On the other hand, we developed an air-stable and reusable cobalt phosphide nanoalloy (nano-Co 2 P) for nitrile hydrogenation . This “P-alloying” imparts not only air stability but also the high ability for hydrogenation to the unstable Co metal.…”

Section: Introductionmentioning

confidence: 99%

Hydrotalcite-Supported Cobalt Phosphide Nanorods as a Highly Active and Reusable Heterogeneous Catalyst for Ammonia-Free Selective Hydrogenation of Nitriles to Primary Amines

Sheng

Yamaguchi

Nakata

et al. 2021

ACS Sustainable Chem. Eng.

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Traditional non-noble-metal catalysts for the hydrogenation of carboxylic acid derivatives have suffered from air instability and inadequate activity, requiring delicate catalyst handling and harsh reaction conditions. Thus, the development of non-noble-metal-based catalysts with both air stability and high activity has recently received much attention. We herein report hydrotalcite-supported cobalt phosphide nanorods (Co2P NR/HT) acting as an air-stable, active, and reusable non-noble-metal-based heterogeneous catalyst for the selective hydrogenation of nitriles to the corresponding primary amines. Co2P NR/HT exhibits a broad substrate generality, including sulfur-containing nitriles as well as aromatic, heteroaromatic, aliphatic, and dinitriles, under mild conditions, typically merely 1 bar of H2 atmosphere. Moreover, the high activity of Co2P NR/HT enabled nitrile hydrogenation under ammonia-free conditions, affording primary amines in high yields. The used Co2P NR/HT catalyst was recoverable and reusable without any significant loss in activity or selectivity, thus demonstrating the high performance of the Co2P NR/HT catalyst. Density functional theory (DFT) calculation results indicate that Co2P NR activates a nitrile at the surface through the back donation of d-electrons in Co2P NR to CN moiety, facilitating the nitrile hydrogenation to the primary amine.

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“…More recently, a highly functional-group tolerant and broad substrate tolerant protocol for the reductive amination of carbonyl-containing compounds and the reductive alkylation of nitriles by carbonyl species has been described by the same team using a 4 wt % Fe/(N)SiC catalyst in the presence of aqueous NH 3 and a 4.7 wt % Co/(N)SiC material, respectively. Their approach to the nanoparticle synthesis, using preformed N-doped SiC matrices to be impregnated in a solution of single-site complexes from the organometallic domain followed by calcination/reduction paths, provided an excellent, robust, and reusable heterogeneous catalyst for the process to occur (Figure ).…”

Section: Catalytic Applicationsmentioning

confidence: 99%

Porous Silicon Carbide (SiC): A Chance for Improving Catalysts or Just Another Active-Phase Carrier?

et al. 2021

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There is an obvious gap between efforts dedicated to the control of chemicophysical and morphological properties of catalyst active phases and the attention paid to the search of new materials to be employed as functional carriers in the upgrading of heterogeneous catalysts. Economic constraints and common habits in preparing heterogeneous catalysts have narrowed the selection of active-phase carriers to a handful of materials: oxide-based ceramics (e.g. Al2O3, SiO2, TiO2, and aluminosilicates–zeolites) and carbon. However, these carriers occasionally face chemicophysical constraints that limit their application in catalysis. For instance, oxides are easily corroded by acids or bases, and carbon is not resistant to oxidation. Therefore, these carriers cannot be recycled. Moreover, the poor thermal conductivity of metal oxide carriers often translates into permanent alterations of the catalyst active sites (i.e. metal active-phase sintering) that compromise the catalyst performance and its lifetime on run. Therefore, the development of new carriers for the design and synthesis of advanced functional catalytic materials and processes is an urgent priority for the heterogeneous catalysis of the future. Silicon carbide (SiC) is a non-oxide semiconductor with unique chemicophysical properties that make it highly attractive in several branches of catalysis. Accordingly, the past decade has witnessed a large increase of reports dedicated to the design of SiC-based catalysts, also in light of a steadily growing portfolio of porous SiC materials covering a wide range of well-controlled pore structure and surface properties. This review article provides a comprehensive overview on the synthesis and use of macro/mesoporous SiC materials in catalysis, stressing their unique features for the design of efficient, cost-effective, and easy to scale-up heterogeneous catalysts, outlining their success where other and more classical oxide-based supports failed. All applications of SiC in catalysis will be reviewed from the perspective of a given chemical reaction, highlighting all improvements rising from the use of SiC in terms of activity, selectivity, and process sustainability. We feel that the experienced viewpoint of SiC-based catalyst producers and end users (these authors) and their critical presentation of a comprehensive overview on the applications of SiC in catalysis will help the readership to create its own opinion on the central role of SiC for the future of heterogeneous catalysis.

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General Synthesis of Secondary Alkylamines by Reductive Alkylation of Nitriles by Aldehydes and Ketones

Cited by 15 publications

References 44 publications

Quick and robust PDF data acquisition using a laboratory single-crystal X-ray diffractometer for study of polynuclear lanthanide complexes in solid form and in solution

Quick and robust PDF data acquisition using a laboratory single-crystal X-ray diffractometer for study of polynuclear lanthanide complexes in solid form and in solution

Hydrotalcite-Supported Cobalt Phosphide Nanorods as a Highly Active and Reusable Heterogeneous Catalyst for Ammonia-Free Selective Hydrogenation of Nitriles to Primary Amines

Porous Silicon Carbide (SiC): A Chance for Improving Catalysts or Just Another Active-Phase Carrier?

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