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Synthesis 2009(9): 1477-1484  
DOI: 10.1055/s-0028-1088122
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Cyclopropenes via 1,2-Elimination of Bromocyclopropanes Catalyzed by Crown Ether

William M. Sherrill, Ryan Kim, Michael Rubin*
Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, Lawrence, KS 66045-758, USA
Fax: +1(785)8645396; e-Mail: mrubin@ku.edu;
Further Information

Publication History

Received 12 November 2008
Publication Date:
14 April 2009 (online)

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Abstract

A new synthetic protocol for the preparation of 3,3-di­substituted cyclopropenes from the corresponding bromocyclopropanes via a base-assisted 1,2-elimination has been developed. Employment of catalytic amounts of 18-crown-6 in ethereal solvents allowed for improved yields, as compared to the classical procedure employing dimethyl sulfoxide, making this protocol applicable to the synthesis of hydrophilic cyclopropenes. The application of this new method for the efficient synthesis of cyclopropene-3-carboxamides, an important class of functionalized 3,3-disubstituted cyclopropenes, is demonstrated. Scope and limitation studies are discussed.

Key words

amides - cyclopropenes - crown ether - eliminations - phase-transfer catalysis

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14

While all the cyclopropenes used in this work have a methyl group at C3, there is no indication that the presented synthetic method is limited to this particular type of substrate. Those reported here were chosen for these studies because they were the most readily available model compounds.