The Roles of 2- and 3-Axial Methoxy Groups in Determining the Stereochemistry of the Complex Metal Hydride Reduction of Cyclohexanones: Examination of the Cieplak Model

The 2- and 3-axially substituted methoxy groups in cyclohexanones exhibit steric hindrance similar to that of the methyl group in LiAlH4 and NaBH4 reductions. The chelate complex formation between the zinc ion and the two oxygens in the molecule was suggested in the zinc borohydride reduction. The r...

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Published inBulletin of the Chemical Society of Japan Vol. 69; no. 11; pp. 3297 - 3303
Main Authors Senda, Yasuhisa, Sakurai, Hiroshi, Nakano, Shigeru, Itoh, Hiroki
Format Journal Article
LanguageEnglish
Published TOKYO The Chemical Society of Japan 01.11.1996
Chemical Soc Japan
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
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Summary:The 2- and 3-axially substituted methoxy groups in cyclohexanones exhibit steric hindrance similar to that of the methyl group in LiAlH4 and NaBH4 reductions. The chelate complex formation between the zinc ion and the two oxygens in the molecule was suggested in the zinc borohydride reduction. The relative reactivities of cyclohexanones in which the 2-axial position is substituted by the methyl or the methoxy group in the LiAlH4 reduction strongly support Cieplak’s proposal, which focuses on the importance of the stabilization of the transition state by anti-periplanar allylic bonds.
ISSN:0009-2673
1348-0634
DOI:10.1246/bcsj.69.3297