Abstract
The TES ether of the C6-hydroxy derivative of naturally occurring epi-jasmonic acid (epi-JA) was designed as epimerization-free equivalent of epi-JA. The TES ether was synthesized from (1R,4S)-4-hydroxycyclopent-2-enyl acetate in 13 steps. The acid part of the ether was activated with ClCO2Bui and subjected to condensation with l-amino acid at room temperature for 48 h. The TES group in the condensation product was removed in HCO2H (0°C, 30 min) and the resulting hydroxyl group was oxidized with Jones reagent (acetone, 0°C, 30 min) to furnish the amino acid conjugate of epi-JA. The amino acids examined are l-isoleucine, l-leucine, l-alanine, l-valine, and d-allo-isoleucine, which afforded the conjugates in 48–68% yields with 89–96% diastereomeric purity over the trans isomers. Similarly, the possible three stereoisomers of epi-JA were condensed with l-isoleucine successfully, producing the corresponding stereoisomers in good yields.
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Acknowledgments
Racemic methyl jasmonate was kindly provided by Zeon Co. Ltd., Japan. This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports, and Culture, Japan.
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Ogawa, N., Kobayashi, Y. Synthesis of the amino acid conjugates of epi-jasmonic acid. Amino Acids 42, 1955–1966 (2012). https://doi.org/10.1007/s00726-011-0925-z
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DOI: https://doi.org/10.1007/s00726-011-0925-z