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Issue 3, 2011
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SPOs as new ligands in Rh(iii) catalyzed enantioselective transfer hydrogenation

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Abstract

The self-assembly of Secondary Phosphine Oxides (SPOs) into anionic bidentate chelates was used to construct unique systems for metal catalyzed transfer hydrogenation of ketones in isopropanol. Chelating bidentate or tridentate ligands were formed by assembly of secondary phosphine oxides through hydrogen bonding in the presence of rhodium trichloride as demonstrated by means of NMR spectroscopy and X-ray diffraction. When a chiral version of an SPO was used in asymmetric transfer hydrogenation of isopropanol and acetophenone, an enantiomeric excess of 89% was achieved. The presence of at least two ligands in the catalytically active species was confirmed by a positive non-linear effect. DFT calculations were applied to characterize several intermediates for the isopropanol dehydrogenation to produce a rhodium hydride complex and acetone. A transition state for the hydrogen-transfer was fully characterized, which revealed that the process occurs via a concerted outer-sphere mechanism.

Graphical abstract: SPOs as new ligands in Rh(iii) catalyzed enantioselective transfer hydrogenation

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Article information


Submitted
19 Oct 2010
Accepted
01 Feb 2011
First published
01 Mar 2011

Catal. Sci. Technol., 2011,1, 401-407
Article type
Paper

SPOs as new ligands in Rh(III) catalyzed enantioselective transfer hydrogenation

P. M. Castro, H. Gulyás, J. Benet-Buchholz, C. Bo, Z. Freixa and P. W. N. M. van Leeuwen, Catal. Sci. Technol., 2011, 1, 401
DOI: 10.1039/C0CY00022A

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