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

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

References

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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.