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Synthesis 2008(23): 3775-3778  
DOI: 10.1055/s-0028-1083231
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Large-Scale Preparation of Enantiomerically Pure (4aR)-(-)-1,4a-Dimethyl-4,4a,7,8-tetrahydronaphthalene-2,5(3H,6H)-dione: A Useful Wieland-Miescher Diketone Analogue

Don Antoine Lanfranchia, Nicolas Baldovinib, Gilles Hanquet*a
a Laboratoire de Stéréochimie associé au CNRS, ECPM, Université Louis Pasteur, 25 rue Becquerel, 67087 Strasbourg, France
Fax: 33(3)90242742; e-Mail: ghanquet@chimie.u-strasbg.fr;
b LCMBA, UMR CNRS 6001, Université de Nice-Sophia Antipolis, Parc Valrose, 06108 Nice Cedex 2, France
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Publication History

Received 26 May 2008
Publication Date:
14 November 2008 (online)

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Abstract

Wieland-Miescher diketone analogue 1 is a widely used precursor for asymmetric synthesis of natural sesquiterpenes and diterpenes. We describe here a large-scale preparation (>125 g batches) of enantiomerically pure compound 1 starting from propionyl chloride and using very simple and cheap reagents. A new one-pot sequence to the intermediate 2-methylcyclohexane-1,3-dione is also described.

Key words

Wieland-Miescher diketone - Dieckmann condensation - thiomethylenation - preferential crystallization

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9

The recrystallized diketone 1 obtained by Snapper et al. had a better ee (93% vs 82%) compared to enantiomerically pure material.¹q