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

Thomas L. Gianetti; Samuel P. Annen; Gustavo Santiso-Quinones; Markus Reiher; Matthias Driess; Hansjörg Grützmacher

doi:10.1002/anie.201509288

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

Thomas L. Gianetti
, Samuel P. Annen
, Gustavo Santiso-Quinones
, Markus Reiher
, Matthias Driess
, Hansjörg Grützmacher

Research output: Contribution to journal › Article › peer-review

79 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	1854-1858
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	55
Issue number	5
DOIs	https://doi.org/10.1002/anie.201509288
State	Published - Jan 26 2016
Externally published	Yes

Keywords

alcohols
catalysis
coupling reactions
dehydrogenation
nitrous oxide
rhodium

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201509288

Cite this

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abstract = "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.",

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T1 - Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols

AU - Gianetti, Thomas L.

AU - Annen, Samuel P.

AU - Santiso-Quinones, Gustavo

AU - Reiher, Markus

AU - Driess, Matthias

AU - Grützmacher, Hansjörg

PY - 2016/1/26

Y1 - 2016/1/26

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AB - 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.

KW - alcohols

KW - catalysis

KW - coupling reactions

KW - dehydrogenation

KW - nitrous oxide

KW - rhodium

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

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

Abstract

Keywords

ASJC Scopus subject areas

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