ポドフィリックアルデヒドの全合成における中間体の反応性の計算化学的考察

The (−)-podophyllic aldehydes (Figure 1) exhibit notable antineoplastic cytotoxicity by apoptosis-inducing activities. In this study, we analyzed the selectivity mechanisms of some important reactions in the asymmetric total synthesis of (+)-podophyllic aldehydes which are enantiomers of the (−)-pod...

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Bibliographic Details
Published in:Journal of Computer Chemistry, Japan Japan, 2017, Vol.16(4), pp.102-105
Main Authors: 三原, 陽子, 森川, 大, 野村, 泰志, 西井, 良典
Format: Article
Language:Japanese
Subjects:
Aldehydes
Apoptosis
Asymmetric total synthesis
Chemical synthesis
Enantiomers
MO method
Molecular orbitals
Nucleophilic addiction
Podophyllic aldehydes
Reduction
Selectivity
Selectivity mechanism
Steric hindrance
Toxicity
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Summary:The (−)-podophyllic aldehydes (Figure 1) exhibit notable antineoplastic cytotoxicity by apoptosis-inducing activities. In this study, we analyzed the selectivity mechanisms of some important reactions in the asymmetric total synthesis of (+)-podophyllic aldehydes which are enantiomers of the (−)-podophyllic aldehydes, by the molecular orbital method. As a result, it was shown that the selectivity of the Grignard reaction in compound 1 (Figure 2) is caused by steric hindrance. Furthermore, it was also indicated that the selectivity of the reduction in compound 2–1 is caused by the localization of LUMO at the reactive site, and the reduction in compounds 2–2 and 2–3 Scheme 2) does not proceed due to the steric hindrance by the trimethoxyphenyl group.
ISSN:1347-1767
1347-3824
DOI:10.2477/jccj.2017-0030