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Synthesis 2006(13): 2143-2146  
DOI: 10.1055/s-2006-942409
PAPER
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of 2-Hydroxy-3,4-dienoates by Oxidation of Zirconium­allenyl Enolates with Dimethyldioxirane

Anja Hoffmann-Röder, Norbert Krause*
University of Dortmund, Organic Chemistry II, Otto-Hahn-Strasse 6, 44227 Dortmund, Germany
Fax: +49(231)7553884; e-Mail: norbert.krause@uni-dortmund.de;
Further Information

Publication History

Received 1 May 2006
Publication Date:
08 June 2006 (online)

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Abstract

The α-hydroxylation of zirconiumallenyl enolates, obtained from β-allenic esters by deprotonation with LDA or LiN(SiMe3)2 and transmetalation with Cp2ZrCl2, with dimethyldioxirane (DMDO) selectively affords 2-hydroxy-3,4-dienoates. The oxidation proceeds usually with high yield and substrate conversion and tolerates even sensitive or unreactive substrates.

Key words

allenes - chirality transfer - enolates - oxidation - zirconium

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1

New address: A. Hoffmann-Röder, Institut für Organische Chemie, Universität Mainz, Duesbergweg 10-14, 55128 Mainz, Germany.

14

The corresponding reaction of allenic ester 1b with LiN(SiMe3)2, Cp2HfCl2 and DMDO furnished product 2b with complete conversion, but in only 38% yield.