Synthesis and Bioactivity of Potassium β-D-Glucopyranosyl 12-Hydroxy Jasmonate and Related Compounds

Abstract

Albizzia saman, a leguminous plant, is known to open its leaves in the daytime and sleep at night with the leaves folded. -D-Glucopyranosyl 12-hydroxyjasmonate (1) was isolated as an endogenous chemical factor controlling this leafmovement. We developed a concise synthesis of optically pure (À)-1 in 9 steps from (+)-2 with a total yield of 58%. Similarly, such analogs of 1 as epi-LCF (13), enantiomer (14), and galactoside (19) were synthesized for a structure activity relationship (SAR) study. The results of this SAR study strongly suggest that the mechanism for the leaf-closing activity of 1 would be different from that of methyl jasmonate, and also suggest the involvement of a different kind of target protein which recognizes the trans-isomer of a jasmonate derivative.

12-Hydroxyjasmonic Acid Glucoside Is a COI1-JAZ-Independent Activator of Leaf-Closing Movement in Samanea saman

“…4A). This result strongly supports the involvement of MTJG in stereospecific recognition of the ligand (2)-LCF (Nakamura et al, 2008a). Next we extended the analysis to other jasmonates and observed that (2)-JA, (2)-12-OH-JA, and (+)-coronatine likewise did not induce shrinking of the extensor motor cells (Fig.…”

“…(2)-LCF, (+)-ent-LCF, and 12-OH-JA were synthesized according to our previous report (Nakamura et al, 2008a). (2)-JA was prepared from commercially available (6)-JA by optical resolution as described (Asamitsu et al, 2006).…”

Trap‐Closing Chemical Factors of the Venus Flytrap (Dionaea muscipulla Ellis)

“…The LMW-TCF was identified as a potassium salt of 1 (2) because the potassium salt of synthetic 1 [12] was as effective as the purified bioactive fraction containing naturally occurring 1 (bioactivity: 3 mm = 2 ng per leaf).…”

“…Interestingly, the sodium salt (3) and free carboxylic acid (1) were one-hundredth as effective as the potassium salt (2). The potassium salts of 12-hydroxy jasmonic acid (4), [12] jasmonic acid (5), [13] and synthetic ent-1 (6) [12] were almost ineffective compared to naturally occurring 2, whereas N-jasmonoyl-l-isoleucine (JA-l-Ile; 7) [14] was weakly effective at 10 mm and 7-iso-1 was also effective at 3 mm. In addition, d-glucose was ineffective at concentrations as high as 300 mm.…”

Chemical Biology of Glycoside-Type Bioactive Substances Controlling Nyctinastic Movement in Leguminous Plants

“…The results of a structure-activity relationship study (16) indicate that the target protein of 1 strictly recognizes the stereochemistry of aglycone. We optically resolved commercially available methyl jasmonate ((±)-3) in order to obtain both enantiomers of the aglycone with a high degree of optical purity in excess of 99.5%ee.…”