Asymmetric Synthesis by the Intramolecular Haloetherification Reaction of Ene Acetal: Discrimination of Prochiral Dienes in Cyclohexane Systems

Hiromichi Fujioka; Naoyuki Kotoku; Yoshinari Sawama; Hidetoshi Kitagawa; Yusuke Ohba; Tsung-Lung Wang; Yasushi Nagatomi; Yasuyuki Kita

doi:10.1248/cpb.53.952

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Asymmetric Synthesis by the Intramolecular Haloetherification Reaction of Ene Acetal: Discrimination of Prochiral Dienes in Cyclohexane Systems

Hiromichi Fujioka, Naoyuki Kotoku, Yoshinari Sawama, Hidetoshi Kitagawa, Yusuke Ohba, Tsung-Lung Wang, Yasushi Nagatomi, Yasuyuki Kita

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Keywords: desymmetrization, cyclohexa-1,4-diene, intramolecular haloetherification, (+)-hydrobenzoin, ene acetal

JOURNAL FREE ACCESS

2005 Volume 53 Issue 8 Pages 952-957

DOI https://doi.org/10.1248/cpb.53.952

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Abstract

A novel asymmetric synthesis of the cyclohexane derivative functionalized by some substituents has been developed from the diene acetals (1), prepared from the corresponding diene aldehyde and (+)-hydrobenzoin. The treatment of 1 with NBS in the presence of MeOCH₂CH₂OH predominantly afforded 2 in a stereoselective manner. Subsequent alkylation of the methoxyethoxy group produced the optically active cyclohexene compounds (3) in good yields. The stereoselective chemical modification of the remaining olefin in 3 was made by OsO₄-oxidation.

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