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Synthesis 2003(6): 0956-0958
DOI: 10.1055/s-2003-38687
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© Georg Thieme Verlag Stuttgart ˙ New York

Simple Large-Scale Preparation of 1,2,3-Tris-Acceptor Substituted Cyclopropanes [1]

Sergei I. Kozhushkov, Andrei Leonov, Armin de Meijere*
Institut für Organische Chemie, Georg-August-Universität Göttingen, Tammannstrasse 2, 37077 Göttingen, Germany
Fax: +49(551)399475; e-Mail: Armin.deMeijere@chemie.uni-goettingen.de;
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Publication History

Received 22 January 2003
Publication Date:
16 April 2003 (online)

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Abstract

Triethyl (1α,2α,3β)cyclopropane-1,2,3-tricarboxylate (3aa), as well as diethyl (4ab) and dimethyl (1α,2β,3α)-1-acetylcyclopropane-2,3-dicarboxylate (4bb) have been prepared on a scale of up to 60 g by Michael initiated ring-closure (MIRC) cyclopropanation of dialkyl fumarates 1a,b with ethyl chloroacetate (2a) and chloroacetone (2b) in 62%, 51% and 56% yield, respectively. For the success of the new procedure it is essential to slowly add (within 5-7 h) the mixture of compounds 1 and 2 to a vigorously stirred suspension of K2CO3 in DMF in the presence of benzyltriethylammonium chloride.

Key words

cyclopropane - cyclizations - Michael additions - MIRC reaction - phase-transfer catalysis

1

Part 93 in the series ‘Cyclopropyl Building Blocks for Organic Synthesis’. For part 92 see: Moszner, N.; Zeuner, F.; Fischer, U. K.; Rheinberger, V.; de Meijere, A.; Bagutski, V. Macromol. Rapid Commun. 2003, in press. Part 91: Gensini, M.; Kozhushkov, S. I.; Frank, D.; VidoviÊ, D.; Brandi, A.; de Meijere, A. Eur. J. Org. Chem. 2003, in press.

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1

Part 93 in the series ‘Cyclopropyl Building Blocks for Organic Synthesis’. For part 92 see: Moszner, N.; Zeuner, F.; Fischer, U. K.; Rheinberger, V.; de Meijere, A.; Bagutski, V. Macromol. Rapid Commun. 2003, in press. Part 91: Gensini, M.; Kozhushkov, S. I.; Frank, D.; VidoviÊ, D.; Brandi, A.; de Meijere, A. Eur. J. Org. Chem. 2003, in press.