Hydrogen-Borrowing and Interrupted-Hydrogen-Borrowing Reactions of Ketones and Methanol Catalyzed by Iridium

Reported herein is the use of catalytic [{Ir(cod)Cl}2] to facilitate hydrogen‐borrowing reactions of ketone enolates with methanol at 65 °C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by prevent...

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Bibliographic Details
Published in:Angewandte Chemie 2015-01, Vol.127 (5), p.1662-1665
Main Authors: Shen, Di, Poole, Darren L., Shotton, Camilla C., Kornahrens, Anne F., Healy, Mark P., Donohoe, Timothy J.
Format: Article
Language:eng ; ger
Subjects:
Catalysis
Catalysts
Chemistry
Conjugates
Interrupts
Iridium
Ketones
Ligands
Methyl alcohol
Michael-Addition
Oxidationen
Phosphines
Synthesemethoden
Wasserstoffübertragungskatalyse
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Summary:Reported herein is the use of catalytic [{Ir(cod)Cl}2] to facilitate hydrogen‐borrowing reactions of ketone enolates with methanol at 65 °C. An oxygen atmosphere accelerates the process, and when combined with the use of a bulky monodentate phosphine ligand, interrupts the catalytic cycle by preventing enone reduction. Subsequent addition of pro‐nucleophiles to the reaction mixture allowed a one‐pot methylenation/conjugate addition protocol to be developed, which greatly expands the range of products that can be made by this methodology. Nur geliehen: [{Ir(cod)Cl}2] erleichtert Wasserstoffübertragungsreaktionen zwischen Ketonenolaten und Methanol bei 65 °C. Eine Sauerstoffatmosphäre unterstützt den Prozess, und der Zusatz eines sperrigen einzähnigen Phosphanliganden verhindert die Enonreduktion und unterbricht den Katalysezyklus. Werden Pronukleophile zum Reaktionsgemisch gegeben, so gelingt eine Methylenierung/konjugierte Addition als Eintopfprotokoll.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201410391