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Synthesis 2012(3): 372-376  
DOI: 10.1055/s-0031-1289600
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© Georg Thieme Verlag Stuttgart ˙ New York

Convenient Synthesis of Ethenylcyclopropane and Some 2-Cyclopropylcyclopropane Derivatives [¹]

Valentin A. Rassadina, Viktor V. Sokolova, Alexander F. Khlebnikova, Nikolay V. Ulina, Sergei I. Kozhushkovb, Armin de Meijere*b
a Department of Chemistry, Saint Petersburg State University, Universitetskii Prospekt 26, Petrodvorets, 198504 St. Petersburg, Russian Federation
b Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Tammannstr. 2, 37077 Göttingen, Germany
Fax: +49(551)23422; e-Mail: ameijer1@uni-goettingen.de;
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Publication History

Received 16 August 2011
Publication Date:
11 November 2011 (online)

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Abstract

Ethenylcyclopropane (5) was prepared from cyclopropyl methyl ketone (1) in four simple, easily scalable steps (bromination, reduction to the bromohydrin, acetylation of the latter, and reductive elimination with Zn/Cu) in an overall yield of 56%. 1-Bromo-2-cyclopropylcyclopropane (7) (approximately 1:1 mixture of cis- and trans-7) was prepared from 5 via the dibromide 6, and from 7 the boronate cis/trans-8 (ratio 1:1) was obtained in 96% yield. Rhodium(II)-catalyzed cyclopropanation of 5 with ethyl diazoacetate gave ethyl 2-cyclopropylcyclopropanecarboxylate (cis/trans-9, ratio 1:1.4) in 80% yield. The latter was also prepared in 79% overall yield by sequential cyclopropanation of buta-1,3-diene with ethyl diazoacetate [under Rh2(OAc)4 catalysis] and diiodomethane/diethylzinc/trifluoroacetic acid. Curtius degradation of 2-cyclopropylcyclopropanecarboxylic acid (obtained by hydrolysis of the ester) gave 2-cyclopropylcyclopropanamine (1:1.2 mixture of cis- and trans-isomers) in 58% yield.

Key words

bromination - reduction - elimination - alkenes - cyclopropanation - small rings

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11

The bromo ketone 2 is extremely lachrymatory, therefore care must be taken in handling it. A one-pot reaction for the bromination and ensuing NaBH4 reduction without isolation of the bromo ketone gave only a poor yield of impure bromohydrin 3.

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