Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols

The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2...

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Bibliographic Details
Published in:Angewandte Chemie 2016-01, Vol.128 (5), p.1886-1890
Main Authors: Gianetti, Thomas L., Annen, Samuel P., Santiso-Quinones, Gustavo, Reiher, Markus, Driess, Matthias, Grützmacher, Hansjörg
Format: Article
Language:eng ; ger
Subjects:
Alcohol
Alcohols
Alkohole
Byproducts
Catalysts
Chemistry
Coupling
Dehydrierungen
Dehydrogenation
Distickstoffoxid
Esters
Hydrogen
Hydrogen storage
Insertion
Katalyse
Kupplungsreaktionen
Ligands
Mathematical analysis
Metals
Nitrous oxide
Nitrous oxides
Oxidation
Oxygen
Rhodium
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Summary:The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin)amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N2 and water are the only by‐products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh−H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate. Wird N2O als Wasserstoffakzeptor in der dehydrierenden Kupplung primärer Alkohole eingesetzt, werden als einzige Beiprodukte N2 und H2O gebildet. Diese Reaktion, die von einem Bis(olefin)amin‐Rhodium(I)‐Komplex unter milden Bedingungen katalysiert wird, zeichnet sich durch eine große Substratbreite aus.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201509288