Synlett 2013; 24(4): 483-486
DOI: 10.1055/s-0032-1318168
letter
© Georg Thieme Verlag Stuttgart · New York

Efficient Synthesis of Cyclopropanecarboxylic Acid Esters Starting from the Conjugate Addition of Lithium Ester Enolates to 1-Chlorovinyl p-Tolyl ­Sulfoxides

Tsutomu Kimura
a   Department of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
,
Yoshiaki Hattori
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   Email: tsatoh@rs.kagu.tus.ac.jp
,
Hitoshi Momochi
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   Email: tsatoh@rs.kagu.tus.ac.jp
,
Nobuhito Nakaya
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   Email: tsatoh@rs.kagu.tus.ac.jp
,
Tsuyoshi Satoh*
a   Department of Chemistry, Faculty of Science, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan
b   Graduate School of Chemical Sciences and Technology, Tokyo University of Science, 12 Ichigaya-funagawara-machi, Shinjuku-ku, Tokyo 162-0826, Japan   Fax: +81(3)52614631   Email: tsatoh@rs.kagu.tus.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 20 December 2012

Accepted after revision: 15 January 2013

Publication Date:
29 January 2013 (online)


Abstract

An efficient synthesis of tert-butyl cyclopropanecarboxylates was achieved in three steps using 1-chlorovinyl p-tolyl sulfoxides as key materials. The conjugate addition of lithium ester enolates to the sulfoxides gave tert-butyl 4-chloro-4-(p-tolylsulfinyl)butanoates in high yield. The p-tolylsulfinyl group in the resultant adducts was then removed by the sulfoxide–magnesium exchange reaction with i-PrMgCl at –60 °C. Cyclization of the desulfinylated products, tert-butyl 4-chlorobutanoates, took place in the presence of NaHMDS in a THF–DMPU mixture to afford tert-butyl cyclopropanecarboxylates in good yield. The asymmetric synthesis of both enantiomers of tert-butyl cyclopropanecarboxylate was successfully achieved using optically active (E)- and (Z)-sulfoxides with high enantiomeric excesses.

Supporting Information

 
  • References and Notes

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