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Keywords: amino acids ´ carbonylations ´ hydantoins ´
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Synthesis and Stereoselective Reactions of
New Stable a-Ferrocenyllithium Derivatives.
An Umpolung of the Ferrocene Reactivity**
Tania Ireland, Juan J. Almena Perea, and
Paul Knochel*
The design of new chiral ligands for asymmetric catalysis is
an important synthetic goal. In particular, ferrocenyl ligands
have attracted considerable attention and numerous synthetic
methods for the preparation of new ferrocenyl derivatives
have been developed.[1] Many useful ferrocenyl ligands can be
prepared by the nucleophilic substitution of readily available
a-ferrocenylcarbinol derivatives of type 1 (Scheme 1).[1, 2]
According to Ugi[2b] these substitutions proceed with reten-
tion of configuration via a chiral cationic intermediate 2 and
lead to products of type 3. Herein we report the umpolung of
this reactivity. It was possible to generate a-ferrocenyllithium
derivatives[3] of type 4 and to react them stereoselectively with
different electrophiles to give the new chiral ferrocenyl
derivatives 5 with complete retention of configuration.
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[*] Prof. Dr. P. Knochel, Dipl.-Chem. T. Ireland
Fachbereich Chemie der Universität
Hans-Meerwein-Strasse, D-35032 Marburg (Germany)
Fax : ( 49)6421-28-21-89
and
Institut für Organische Chemie der Universität
Butenandtstrasse 5 ± 13, D-81377 Munich (Germany)
Dr. J. J. Almena Perea
Degussa-Hüls AG, Abteilung Spezialchemikalien
D-63403 Hanau (Germany)
[**] We thank the DFG (SFB 260, Graduiertenkolleg, Leibniz-program)
and the Fonds der Chemischen Industrie for generous support. We
thank the Degussa-Hüls AG and Chemetall GmbH for the generous
gift of chemicals. J.J.A.P. thanks the Alexander von Humboldt
Foundation for a post-doctoral fellowship.
Angew. Chem. Int. Ed. 1999, 38, No. 10
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