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Synthesis 2011(5): 769-777  
DOI: 10.1055/s-0030-1259430
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthetic Studies towards Optically Active 13-Oxyingenol via Asymmetric ­Cyclopropanation

Ichiro Hayakawa, Yamato Miyazawa, Takayuki Ohyoshi, Yuki Asuma, Kenta Aoki, Hideo Kigoshi*
Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Ibaraki 305-8571, Japan
Fax: +81(29)8534313; e-Mail: kigoshi@chem.tsukuba.ac.jp;
Further Information

Publication History

Received 16 November 2010
Publication Date:
31 January 2011 (online)

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Abstract

The enantioselective synthesis of a seven-membered enone compound, the key intermediate of our previous synthesis of the inside-outside framework of 13-oxyingenol in racemic form, was achieved by using asymmetric cyclopropanation and reductive deoxygenation as key steps.

Key words

13-oxyingenol - asymmetric cyclopropanation - chiral aza-semicorrin ligand - reductive deoxygenation - intramolecular ­aldol reaction

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1

Research fellow of the Japan Society for the Promotion of Science (JSPS).

13

This asymmetric synthesis of seven-membered enone (-)-7 had a low yield in comparison with our previous approach in racemic form, possibly because of the small reaction scale. The detailed experimental procedures for the seven-membered enone (±)-7 6 in multigram scale are given in the experimental section.