Asymmetric Synthesis in the Methoxy-mercuration of α, β-Unsaturated Esters
- 1 February 1967
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 40 (2) , 373-378
- https://doi.org/10.1246/bcsj.40.373
Abstract
The methoxy-mercuration of (−)-menthyl crotonate, cinnamate, and β-methylcinnamate resulted in partial asymmetric syntheses of the corresponding β-methoxylated derivatives, (−)-R-β-methoxybutyric acid, (−)-S-β-methoxy-β-phenylpropyl alcohol, and (−)-S-β-methoxy-β-phenylbutyl alcohol. The results suggested an ionic mechanism involving a cyclic mercurinium ion as an intermediate, formed by the electrophilic attack of mercuric acetate from the least-hindered side of the double bond in the Cram-Prelog model of the systems, followed by the attack of the methoxy anion from the opposite side. The reaction mechanism leading to the predominant enantiomers was discussed.Keywords
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