Asymmetric Pauson-Khand-type Reaction Mediated by Rh(I)
Catalyst at Ambient Temperature
Dong Eun Kim,† In Su Kim,† Virginie Ratovelomanana-Vidal,*,‡ Jean-Pierre Geneˆt,*,‡ and
Nakcheol Jeong*,†
Department of Chemistry, Korea UniVersity, Seoul, 136-701, Korea, and Laboratoire de Synthe`se Se´lectiVe
Organique et Produits Naturels, Ecole Nationale Supe´rieure de Chimie de Paris, 11 rue Pierre et
Marie Curie, 75231 Paris Cedex 05, France
njeong@korea.ac.kr; jean-pierre-genet@enscp.fr; Virginie-Vidal@enscp.fr
ReceiVed June 9, 2008
An efficient asymmetric PKR mediated by Rh(I) catalyst at ambient temperature was developed.
The reaction utilizing a Rh(I) catalyst bearing a (R)-3,5-diMeC4H4-BINAP ligand at 18-20 °C under
a reduced partial pressure of CO (0.1 atm) provided PKR products in high chemical yield as well as
high enantioselectivity.
Introduction
some limitations were encountered with certain classes of
substrates. Systematic efforts to perfect this protocol in terms
of the chemical yield and enantioselectivity have since been
made by us7 and others.
In recent years, a great deal of research has been devoted to
the asymmetric catalytic Pauson-Khand reaction (denoted as
the APKR hereafter).1,2 Various versions of the enantioselective
PK-type reaction using cobalt,3 titanium,4 rhodium,5 and iri-
dium6 together with chiral ligands have been published.
Many years ago, we described the first rhodium-catalyzed
enantioselective PKR under a CO atmosphere in the presence
of the atropisomeric BINAP ligand (Scheme 1).5a,b These early
results were promising in terms of the enantioselectivity, but
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† Korea University.
‡ Ecole Nationale Supe´rieure de Chimie de Paris.
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10.1021/jo801236c CCC: $40.75
Published on Web 09/18/2008
2008 American Chemical Society
J. Org. Chem. 2008, 73, 7985–7989 7985