Solution and Gas‐Phase Reactivity of Me12Fe8− and Related Cluster Ions

Parchomyk, Tobias; Koszinowski, Konrad

doi:10.1002/chem.201605602

Cited by 15 publications

(14 citation statements)

References 78 publications

(54 reference statements)

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“…53 Other multidentate amines show similar behavior. 65 In line with this finding, Parchomyk and Koszinowski did not observe TMEDA binding to any anionic ferrate complexes, 59,60 but only to magnesium cations. 60 Furthermore, the addition of TMEDA to the in situ formed organoiron species resulted in the disappearance of the higher aggregates.…”

Section: Transmetallation and Activation Of The Iron Precatalystsupporting

confidence: 58%

“…71b Similarly, Parchomyk and Koszinowski found the cluster ion Me 12 Fe 8 to exchange methyl groups with its perdeuterated analogue (Scheme 11). 59 This exchange possibly involves the simultaneously observed Me 13 Fe 8…”

Section: Short Review Syn Thesismentioning

confidence: 94%

“…60 Furthermore, the addition of TMEDA to the in situ formed organoiron species resulted in the disappearance of the higher aggregates. 59,60 Unlike TMEDA, the Bopa pincer ligands employed by the Hu group (Scheme 9) at least partly bound to an iron(II) center to afford a catalytically active species, which the authors assigned as Ph 2 Fe(Bopa) -. 66 Several protocols for iron-catalyzed cross-coupling make use of phosphines as ligands.…”

Section: Transmetallation and Activation Of The Iron Precatalystmentioning

confidence: 99%

“…69 When Parchomyk and Koszinowski treated an iron(II) complex of 1,2-bis(diphenylphosphino)benzene (dppbz) with 4 equivalents of phenylmagnesium chloride, they observed the dinuclear iron(I) ate complex Ph 3 Fe 2 (dppbz)by ESI mass spectrometry, along with further low-valent phenylferrates containing the dppbz ligand. 59 The finding of analogous complexes of triphenylphosphine, but not of 1,2-bis(diphenylphosphino)ethane (dppe) or 1,3-bis(diphenylphosphino)propane (dppp), indicated the importance of electronic effects for stabilizing low-valent anionic organoferrates.…”

Section: Transmetallation and Activation Of The Iron Precatalystmentioning

confidence: 99%

“…A further type of dynamic behavior is given by redox disproportionation. The common observation of tetraorganyliron(III) ate complexes R 4 Fein the presence of a Grignard reagent and, thus, under reducing conditions 53,56,59,60,62 suggests that these species result from the disproportionation of transient Fe(II) species (Scheme 12). 53,60,62 The detection of the concomitantly formed iron(I) proved more difficult until very recently Lefèvre and coworkers found such evidence on the basis of EPR spectroscopic measurements.…”

Section: Scheme 11mentioning

confidence: 99%

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Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Parchomyk

Koszinowski

2017

Synthesis

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Iron-catalyzed cross-coupling reactions provide a promising way to form new carbon–carbon bonds and build up molecular complexity. This short review presents recent advances in the synthetic application of these reactions as well as in the elucidation of their mechanism. It also highlights remaining problems and aims at pointing out ways toward possible remedies.1 Introduction2 Synthesis: Recent Accomplishments and Unsolved Problems2.1 Substrate Scope: Electrophiles2.2 Substrate Scope: Nucleophiles2.3 Catalyst Activity and Chemoselectivity2.4 Stereoselectivity2.5 Practical Aspects3 Mechanism: Recent Insights and Open Questions3.1 Transmetallation and Activation of the Iron Precatalyst3.2 Coupling via Oxidative Addition and Reductive Elimination3.3 Coupling via C–X Bond Homolysis and Radical Rebound3.4 Coupling via Bimolecular C–X Bond Homolysis3.5 Other Reactions of Organoiron Species with Electrophiles4 Toward Rational Reaction Improvement5 Conclusion

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Section: Transmetallation and Activation Of The Iron Precatalystsupporting

confidence: 58%

Section: Short Review Syn Thesismentioning

confidence: 94%

Section: Transmetallation and Activation Of The Iron Precatalystmentioning

confidence: 99%

Section: Transmetallation and Activation Of The Iron Precatalystmentioning

confidence: 99%

Section: Scheme 11mentioning

confidence: 99%

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Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Parchomyk

Koszinowski

2017

Synthesis

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Eisenkatalysierte Kreuzkupplungen in der Synthese von Pharmazeutika: Streben nach Nachhaltigkeit

Piontek¹,

Bisz²,

Szostak

2018

Angewandte Chemie

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Der Mangel an Edelmetallen hat eine Suche nach nachhaltigen Strategien für metallkatalysierte Kreuzkupplungen ausgelöst. Die Entwicklung neuer Katalysemethoden unter Verwendung von Eisen ist wegen der geringen Kosten, leichten Verfügbarkeit und sehr geringen Toxizität von Eisen hoch attraktiv. In den letzten Jahren haben nachhaltige Methoden für eisenkatalysierte Kreuzkupplungen den kritischen Bereich der pharmazeutischen Forschung erreicht. Insbesondere ist Eisen eines der sehr wenigen unedlen Metalle, deren praktischer Einsatz in industriellen Kreuzkupplungen im Kilogrammmaßstab erfolgreich erprobt wurde. In diesem Kurzaufsatz wollen wir die strategischen Vorteile der Verwendung von Eisenkatalysatoren als umweltfreundliche und nachhaltige Alternative zu Edelmetallen in Kreuzkupplungen für die Synthese von Pharmazeutika kritisch beleuchten. Wir bieten eine Einführung in die grundlegenden Aspekte der Eisenkatalyse, heben Bereiche mit Verbesserungspotenzial hervor und zeigen neue Richtungen auf, die in Zukunft erforscht werden sollten.

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Iron‐Catalyzed Cross‐Couplings in the Synthesis of Pharmaceuticals: In Pursuit of Sustainability

2018

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The scarcity of precious metals has led to the development of sustainable strategies for metal-catalyzed cross-coupling reactions. The establishment of new catalytic methods using iron is attractive owing to the low cost, abundance, ready availability, and very low toxicity of iron. In the last few years, sustainable methods for iron-catalyzed cross-couplings have entered the critical area of pharmaceutical research. Most notably, iron is one of the very few metals that have been successfully field-tested as highly effective base-metal catalysts in practical, kilogram-scale industrial cross-couplings. In this Minireview, we critically discuss the strategic benefits of using iron catalysts as green and sustainable alternatives to precious metals in cross-coupling applications for the synthesis of pharmaceuticals. The Minireview provides an essential introduction to the fundamental aspects of practical iron catalysis, highlights areas for improvement, and identifies new fields to be explored.

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Solution and Gas‐Phase Reactivity of Me₁₂Fe₈⁻ and Related Cluster Ions

Cited by 15 publications

References 78 publications

Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Iron-Catalyzed Cross-Coupling: Mechanistic Insight for Rational Applications in Synthesis

Eisenkatalysierte Kreuzkupplungen in der Synthese von Pharmazeutika: Streben nach Nachhaltigkeit

Iron‐Catalyzed Cross‐Couplings in the Synthesis of Pharmaceuticals: In Pursuit of Sustainability

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