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Angewandte
Communications
Chemie
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h). Cycloalkyl ketones with small ring sizes are herein more
readily hydrogenated than ketones with larger ring systems,
resulting in only 58% yield of 5h despite the use of 1 mol%
pre-catalyst. The five-membered ring of 1-indanone also
required the higher than usual pre-catalyst loading of
1 mol%, but was quantitatively hydrogenated to the corre-
sponding alcohol 5i.
=
[6] Other examples for efficient Co based C O bond hydrogenation
In summary, we introduced a highly active and easy to
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=
synthesize Mn based C O bond hydrogenation catalyst. The
easy modification of the used multidentate ligands makes the
catalyst family attractive for fast catalyst identification.
Manganese is the third most abundant transition metal in
the Earth’s crust and we developed a Mn catalyst, which
hydrogenates various ketones quantitatively in 4h with only
0.1 mol% catalyst loading. The substrate scope is broad since
aryl–alkyl, diaryl, dialkyl, and cycloalkyl ketones can be
hydrogenated smoothly. In addition, we see an impressive
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=
functional group tolerance. Hydrogenation of C O bonds
proceeds selectively in the presence of a non-shielded olefin,
a nitrile, or a nitro group.
Most importantly, we feel that in Mn hydrogenation
catalysis the combination of the multidentate ligand, the
oxidation state of the metal, and the choice of the right
ancillary ligand is crucial to give high activity. This observa-
tion emphasizes an advantage of homogeneous catalysis in
the application of base metals as active sites. For coordination
compounds, a fine-tuning of a complex coordination environ-
ment is easily accomplished in comparison to enzyme
catalysis and/or heterogeneous catalysis.
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[10] Selected examples of recently published manuscripts: a) parallel
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Acknowledgements
This work was supported by the Deutsche Forschungsge-
meinschaft (KE 756/23-2 28-1).
Keywords: alcohols · base metals · hydrogenation · manganese ·
PNP ligands
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[16] CCDC 1499551 (2a) and 1499552 (3b) contain the supplemen-
tary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via Cambridge Crystallographic Data Centre.
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Received: June 27, 2016
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Angew. Chem. Int. Ed. 2016, 55, 1 – 5
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