Herein, we report the successful transformation of a 1st generation Grubbs metathesis catalyst into an asymmetric transfer hydrogenation (ATH) catalyst. Upon addition of a chiral amine ligand, an alcohol and a base, the 1st generation Hoveyda-Grubbs catalyst (HG-I) was found to promote the enantioselective reduction of acetophenone to 1-phenylethanol. After optimizing the order of addition and the reaction conditions, the substrate scope was assessed leading to enantiomeric excesses up to 97% ee. NMR experiments were run in order to get information about the in situ-generated ATH catalyst. Furthermore, the possibility to perform olefin metathesis and ketone transfer hydrogenation sequentially in one pot was demonstrated, and the first tandem olefin metathesis-ketone asymmetric transfer hydrogenation was carried out.

Asymmetric Transfer Hydrogenation of Ketones with Modified Grubbs Metathesis Catalysts: On the Way to a Tandem Process

PIARULLI, UMBERTO;
2016-01-01

Abstract

Herein, we report the successful transformation of a 1st generation Grubbs metathesis catalyst into an asymmetric transfer hydrogenation (ATH) catalyst. Upon addition of a chiral amine ligand, an alcohol and a base, the 1st generation Hoveyda-Grubbs catalyst (HG-I) was found to promote the enantioselective reduction of acetophenone to 1-phenylethanol. After optimizing the order of addition and the reaction conditions, the substrate scope was assessed leading to enantiomeric excesses up to 97% ee. NMR experiments were run in order to get information about the in situ-generated ATH catalyst. Furthermore, the possibility to perform olefin metathesis and ketone transfer hydrogenation sequentially in one pot was demonstrated, and the first tandem olefin metathesis-ketone asymmetric transfer hydrogenation was carried out.
2016
http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1615-4169
asymmetric catalysis; metathesis; ruthenium; tandem catalysis; transfer hydrogenation; Catalysis; Organic Chemistry
Renom Carrasco, Marc; Gajewski, Piotr; Pignataro, Luca; De Vries, Johannes G.; Piarulli, Umberto; Gennari, Cesare; Lefort, Laurent
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/2061554
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