Synlett 2004(1): 93-96  
DOI: 10.1055/s-2003-43373
LETTER
© Georg Thieme Verlag Stuttgart · New York

From Allylic Alcohols to Aldols via a Novel, Efficient Reaction Catalyzed by Ni-Complexes

David Cuperly, Christophe Crévisy, René Grée*
ENSCR, laboratoire de Synthèses et Activations de Biomolécules, UMR CNRS 6052, 35700 Rennes, France
Fax: +33(2)23238108; e-Mail: rene.gree@ensc-rennes.fr;
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Publikationsverlauf

Received 10 October 2003
Publikationsdatum:
04. Dezember 2003 (online)

Abstract

Allylic alcohols react with aldehydes, in an atom economic aldol-type reaction, in the presence of a catalytic amount of (dppe)NiHCl/MgBr2 mixture. This reaction occurs in good to excellent yields with total regiocontrol and very high chemo control under mild conditions. It is compatible with various types of aldehydes including very bulky ones.

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The stereoisomeric ratios were established by 1H NMR on the crude reaction mixture. The relative stereochemistries were attributed by comparison with literature data or according to the following empirical rule: The C of the CHOH group is deshielded in the anti-adduct compared to the syn-adduct and the H of the CHOH group is shielded in the anti-adduct compared to the syn-adduct.