A New Coupling Reaction of Alkyl Iodides with Electron Deficient Alkenes Using Nickel Boride (cat.)−Borohydride Exchange Resin in Methanol

Sim, Tae Bo; Choi, Jieun; Joung, Meyoung Ju; Yoon, Nung Min

doi:10.1021/jo961751f

Cited by 37 publications

(16 citation statements)

References 12 publications

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“…Court et al anchored an optically active b-amino alcohol to nickel boride, which afforded a heterogeneous catalyst for efficient enantioselective reduction of ketones [122][123][124]. Now, the metal-metalloid amorphous alloy can also be applied in the partial oxidation of methane to syngas [130], ethanol dehydrogenation [96,97], synthesis of hydrogen peroxide from carbon monoxide, water and oxygen [131], catalytic growth of carbon nanofiber [83] or boron nitride tube [132][133][134][135], desulphurization [136][137][138], reduction of alkyl halides or nitro compounds [139][140][141], coupling reaction of alkenes [142,143], and hydrogen fuel cell [144,145]. On the other hand, amorphous MP and MB alloys have been widely used as hydrogen storage materials [146,147] and anticorrosive materials [94].…”

Section: Hydrogenation and Other Applicationsmentioning

confidence: 99%

Advances in chemical synthesis and application of metal-metalloid amorphous alloy nanoparticulate catalysts

Zhang

et al. 2007

Front. Chem. Eng. China

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This paper reviews the advances in the chemical synthesis and application of metal-metalloid amorphous alloy nanoparticles consisting of transition metal (M) and metalloid elements (B, P). After a brief introduction on the history of amorphous alloy catalysts, the paper focuses on the properties and characterization of amorphous alloy catalysts, and recent developments in the solution-phase synthesis of amorphous alloy nanoparticles. This paper further outlines the applications of amorphous alloys, with special emphasis on the problems and strategies for the application of amorphous alloy nanoparticles in catalytic reactions. History of amorphous alloy catalystAmorphous alloys have been extensively investigated internationally over the last 50 years largely spurred by their unique electronic, magnetic and surface properties and their increasing utility in a broad range of applications [1,2]. The amorphous alloy nanoparticles have gained increasing attention as novel catalytic materials since 1980, with the unique isotropic structure and high concentration of coordinatively unsaturated sites leading to catalytic activity and selectivity superior to their crystalline counterparts [3]. Especially, amorphous alloys chemically reduced by borohydride (BH 4 − ) and hypophosphite (H 2 PO 2 − ) have nanosized morphology and consequently higher surface area and activity than those prepared by the quenching method [4][5][6][7][8]. It has been regarded that the amorphous alloy catalyst can be a potential alternative to Raney nickel or noble metal catalyst in catalytic hydrogenation. Raney nickel has shown many serious disadvantages, such as short lifetimes due to poor sulfur resistance and environmental pollution caused by alkaline leaching during preparation. In contrast, the amorphous alloy nanoparticulate catalysts are inexpensive, environmentally benign, and effective catalytic materials.For the chemical synthesis of metal-metalloid amorphous alloy catalysts, Brown et al. and Paul et al. found that the NiB particles reduced by sodium borohydride in water or ethanol solution showed excellent catalytic activity and selectivity in many hydrogenation reactions [9][10][11][12][13][14][15]. After that, and Chen et al. [21][22][23][24] studied the mechanism of borohydride reduction and the relation between properties and preparation conditions. On the other hand, Deng and coworkers have been interested in studying the properties of amorphous alloy particles and the application of metal boron (MB) and metal phosphorus (MP) amorphous alloys for catalytic hydrogenation [25-37]. Dragieva et al. focused on developing amorphous alloys as electrode or catalytic oxidation materials [38-43], while Chen and coworkers prepared MPB alloy nanoparticle catalysts for various selective hydrogenation reactions [44-50]. Amorphous alloy nanoparticulate catalysts have been widely studied by different research groups in China [51-60]. Among them, our group has attempted to develop NiB and NiP industrial amorphous alloy catalysts in various catalyt...

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Section: Hydrogenation and Other Applicationsmentioning

confidence: 99%

Advances in chemical synthesis and application of metal-metalloid amorphous alloy nanoparticulate catalysts

Zhang

et al. 2007

Front. Chem. Eng. China

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“…Nickel( II ) boride BER 10 has proven to be a substitute for polymer‐bound tributyltin hydride (see also Scheme ), because it promotes the radical addition of alkyl iodides to electron‐deficient alkenes (Scheme ) 146. With α ‐bromo carboxylic acids 10 has been employed for generating C‐radicals which react with aliphatic alkenes and vinyl ethers 147…”

Section: Stoichiometric Polymer‐supported Reagentsmentioning

confidence: 99%

Functionalized Polymers-Emerging Versatile Tools for Solution-Phase Chemistry and Automated Parallel Synthesis

Kirschning

Monenschein

Wittenberg

2001

Angew. Chem. Int. Ed.

380

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As part of the dramatic changes associated with the need for preparing compound libraries in pharmaceutical and agrochemical research laboratories, industry searches for new technologies that allow for the automation of synthetic processes. Since the pioneering work by Merrifield polymeric supports have been identified to play a key role in this field however, polymer‐assisted solution‐phase synthesis which utilizes immobilized reagents and catalysts has only recently begun to flourish. Polymer‐assisted solution‐phase synthesis has various advantages over conventional solution‐phase chemistry, such as the ease of separation of the supported species from a reaction mixture by filtration and washing, the opportunity to use an excess of the reagent to force the reaction to completion without causing workup problems, and the adaptability to continuous‐flow processes. Various strategies for employing functionalized polymers stoichiometrically have been developed. Apart from reagents that are covalently or ionically attached to the polymeric backbone and which are released into solution in the presence of a suitable substrate, scavenger reagents play an increasingly important role in purifying reaction mixtures. Employing functionalized polymers in solution‐phase synthesis has been shown to be extremely useful in automated parallel synthesis and multistep sequences. So far, compound libraries containing as many as 88 members have been generated by using several polymer‐bound reagents one after another. Furthermore, it has been demonstrated that complex natural products like the alkaloids (±)‐oxomaritidine and (±)‐epimaritidine can be prepared by a sequence of five and six consecutive polymer‐assisted steps, respectively, and the potent analgesic compound (±)‐epibatidine in twelve linear steps ten of which are based on functionalized polymers. These developments reveal the great future prospects of polymer‐assisted solution‐phase synthesis.

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“…Nickel( II )‐dotiertes, an polymeren Träger gebundenes Borhydrid 10 verhält sich insofern ähnlich wie Polymer‐gebundenes Tributylzinnhydrid (siehe auch Schema ), als es die radikalische Addition von Alkyliodiden an elektronenarme Alkene erlaubt (Schema ) 146. Aus α ‐Bromcarbonsäuren können mit 10 C‐Radikale erzeugt werden, die mit aliphatischen Alkenen und Vinylethern reagieren können 147…”

Section: Polymer‐verankerte Reagentien Die Nicht In Katalytischenunclassified

Funktionalisierte Polymere - zukunftsträchtige Werkzeuge für die Chemie in Lösung und die automatisierte Parallelsynthese

2001

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Der Bedarf der pharmazeutischen und agrochemischen Forschung an Substanzbibliotheken hat eine verstärkte Suche der Industrie nach neuen Technologien, die die Automatisierung von Syntheseprozessen erlauben, zur Folge. Seit den Pionierarbeiten von Merrifield spielen polymere Trägermaterialien eine Schlüsselrolle in diesem Gebiet, doch werden jetzt immer häufiger Polymer‐unterstützte Synthesen in Lösung unter Nutzung von funktionalisierten Polymeren als Träger für Reagentien oder Katalysatoren untersucht. Die Polymer‐unterstützte Synthese in Lösung bietet gegenüber der konventionellen Lösungschemie vielerlei Vorteile, z. B. die leichte Abtrennbarkeit der Polymer‐gebundenen Spezies vom Reaktionsgemisch durch Filtration oder Waschen sowie die Möglichkeit, das Reagens im Überschuss einzusetzen, um einen vollständigen Umsatz ohne Probleme bei der Aufarbeitung zu erzielen. Außerdem lassen sich mit diesem Konzept auf sehr einfache Weise Durchflussreaktoren betreiben. Verschiedene Strategien zum stöchiometrischen Einsatz von funktionalisierten Polymeren wurden entwickelt. Neben Reagentien, die kovalent oder ionisch an den polymeren Träger gebunden sind und in Anwesenheit eines geeigneten Substrats in Lösung gehen, spielen Abfangreagentien (scavenger) eine zunehmend größere Rolle bei der Reinigung von Reaktionsmischungen. Das Konzept funktionalisierter Polymere für die Synthese in Lösung erweist sich als nützlich für die automatisierte Parallelsynthese und in der Durchführung von mehrstufigen Synthesesequenzen. Bisher konnten Bibliotheken mit bis zu 88 Verbindungen durch den Einsatz mehrerer, sukzessiv verwendeter Polymer‐gebundener Reagentien erzeugt werden. Weiterhin wurden erstmals komplexe Naturstoffe wie die Alkaloide (±)‐Oxomaritidin und (±)‐Epimaritidin durch eine Reihe von fünf und sechs aufeinander folgenden, durch Polymer‐verankerte Reagentien vermittelten Reaktionen synthetisiert. Noch bemerkenswerter erscheint die Herstellung des potenten Analgetikums (±)‐Epibatidin, bei der zehn von zwölf linearen Stufen durch funktionalisierte Polymere realisiert wurden. Diese Entwicklungen zeigen die große Zukunft der Polymer‐unterstützten Synthese in Lösung auf.

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A New Coupling Reaction of Alkyl Iodides with Electron Deficient Alkenes Using Nickel Boride (cat.)−Borohydride Exchange Resin in Methanol

Cited by 37 publications

References 12 publications

Advances in chemical synthesis and application of metal-metalloid amorphous alloy nanoparticulate catalysts

Advances in chemical synthesis and application of metal-metalloid amorphous alloy nanoparticulate catalysts

Functionalized Polymers-Emerging Versatile Tools for Solution-Phase Chemistry and Automated Parallel Synthesis

Funktionalisierte Polymere - zukunftsträchtige Werkzeuge für die Chemie in Lösung und die automatisierte Parallelsynthese

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