Chemoselective Activities of Fe(III) Catalysts in the Hydrofunctionalization of Allenes

Jung, Minwoo; Kim, Won Sun; Shin, Ye Ho; Jin, Ha Jeong; Kim, Young Sam; Kang, Eun Joo

doi:10.1021/ol303021d

Cited by 39 publications

(20 citation statements)

References 40 publications

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“…[49] Furthermore,t he triggered release of the metal ion from ferrocene can be used to induce acolor change and/ or the formation of apigment for, for example,analytical and medical applications.I tc an be envisaged to use this unique type of polymer scission also in catalysis,a si ron ions are highly active catalysts for different organic reactions,such as intramolecular hydroalkoxylation and hydroamination reactions of allenes. [50] These materials have the potential to mechano-generate free base in solution, exploiting the cyclopentadienyl anion, formed after the ferrocene breaking, even though we cannot exclude rapid protonation or the formation of CpC,considering that during sonication experiments radical species can also be easily generated. [8,44] Further studies are under way to determine the scission mechanism of the metallocene and the use of such am etal-release-on-demand system for applications in catalysis.…”

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confidence: 99%

Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

et al. 2018

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The introduction of mechanophores into polymers makes it possible to transduce mechanical forces into chemical reactions that can be used to impart functions such as self-healing, catalytic activity, and mechanochromic response. Here, an example of mechanically induced metal ion release from a polymer is reported. Ferrocene (Fc) was incorporated as an iron ion releasing mechanophore into poly(methyl acrylate)s (PMAs) and polyurethanes (PUs). Sonication triggered the preferential cleavage of the polymers at the Fc units over other bonds, as shown by a kinetic study of the molar mass distribution of the cleaved Fc-containing and Fc-free reference polymers. The released and oxidized iron ions can be detected with KSCN to generate the red-colored [Fe(SCN) (H O) )] complex or reacted with K [Fe(CN) ] to afford Prussian blue.

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Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

et al. 2018

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“…Eine weitere Anwendung könnte in der Katalyse liegen, da Eisenionen hochaktive Katalysatoren für verschiedene organische Reaktionen darstellen, z. B. die intramolekulare Hydroalkoxylierung und Hydroaminierungsreaktionen von Allenen . Die oben beschriebenen Polymere haben außerdem das Potential, mechanisch induziert freie Basen in Lösung zu bilden, und zwar in Form des Cyclopentadienyl‐Anions, welches wahrscheinlich nach dem Bindungsbruch des Ferrocens gebildet wird, obwohl sich eine schnelle Protonierung des Anions oder ein homolytischer Bindungsbruch nicht ausschließen lassen .…”

Section: Methodsunclassified

Getriggerte Freisetzung und Oxidation von Metallionen: Ferrocen als neuer Mechanophor in Polymeren

Giannantonio¹,

Ayer

Verde‐Sesto

et al. 2018

Angewandte Chemie

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Die Einführung von Mechanophoren in Polymere erlaubt es,m echanische Kräfte in chemische Reaktionen umzuwandeln, was wiederum zu neuen Funktionalitäten führen kann, wie beispielsweise Selbstheilung,k atalytischer Aktivität oder mechanochromen Eigenschaften. Diese Zuschrift beschreibt die mechanisch induzierte Freisetzungv on Metallionen aus in Polymerketten (z. B. Poly(methylacrylat) und Polyurethan) eingebetteten Ferrocen-Einheiten (Fc). Durch die Bestrahlung mit Ultraschall werden diese Sollbruchstellen bevorzugt gespalten, wie anhand kinetischer Molmassenbestimmungen von Fc-haltigen und Fc-freien Polymeren gezeigt werden konnte.D ie freigesetzten und oxidierten Eisenionen konnten durch die Umsetzung mit KSCN oder K 4 [Fe(CN) 6 ]als typisch roter [Fe(SCN) n (H 2 O) 6Àn )] (3Àn)+ Komplex, bzw.a ls Preußischblau nachgewiesen werden.

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“…[30] Using cyclopentyl-substituted allenyl alcohol 31 (R 3 to R 4 = cyclopentyl, X = O) as a test substrate, FeCl 3 -catalysed cyclisation gave tetrahydropyran products 32 and 33 in excellent yields (Scheme 12). At low temperatures, or over short reaction times, 2-vinyltetrahydropyran product 32 was formed selectively, whereas high temperatures and increased reaction times resulted in double-bond isomerisation to give 2-allyl tetrahydropyran 33.…”

Section: Addition Of N O and S Nucleophiles To Alkenes And Alkynesmentioning

confidence: 99%

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

2014

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The metal‐catalysed hydrofunctionalisation of alkenes and alkynes provides a convenient and atom‐economic route to diversely functionalised products with control of regio‐, chemo‐ and stereoselectivity. As one of the most abundant elements on earth, iron offers a level of sustainable and long‐term availability that is uncommon for most transition metals. Although iron is commonly found in the oxidation states of +2 and +3, the use of redox‐active ligands has allowed the synthesis and application of low oxidation state iron complexes in catalysis. A broad range of hydrofunctionalisation reactions have been developed by using iron catalysts in a wide variety of oxidation states. Intense development over the past decade has resulted in the development of iron‐catalysed hydroamination, hydroalkoxylation, hydrocarboxylation, hydrothiolation, hydrovinylation, hydrosilylation, hydroboration, hydrophosphination, hydromagnesiation and carbonylation reactions, amongst others. With the field still in its infancy, there is great potential for further developments in the mechanistic understanding and synthetic and industrial applicability of these processes.

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Chemoselective Activities of Fe(III) Catalysts in the Hydrofunctionalization of Allenes

Cited by 39 publications

References 40 publications

Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

Triggered Metal Ion Release and Oxidation: Ferrocene as a Mechanophore in Polymers

Getriggerte Freisetzung und Oxidation von Metallionen: Ferrocen als neuer Mechanophor in Polymeren

Iron‐Catalysed Hydrofunctionalisation of Alkenes and Alkynes

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