Methyl -jasmonate

Allyl aryl ethers are used for allylation under basic conditionsfh], but they can be cleaved under neutral conditions. Formation of the five-membered ring compound 284 based on the cyclization of 283 has been applied to the syntheses of methyl jasmonate (285)[15], and sarkomycin[169]. The trisannulation reagent 286 for steroid synthesis undergoes Pd-catalyzed cyclization and aldol condensation to afford CD rings 287 of steroids with a functionalized 18-methyl group 170]. The 3-vinylcyclopentanonecarboxylate 289, formed from 288, is useful for the synthesis of 18-hydroxyestrone (290)[I7I]. 

Of the 11 compounds which constitute approximately 86% of jasmin volatiles, only benzyl acetate, i7t-jasmone (18), and methyl jasmonate possess the characteristic odor of jasmin. Trace components including i7t-j asrnin lactone [34686-71-0] (20) (0.9%) andmethyl ( /-jasmonate (6) (0.1%) are the key contributors to the jasmin odor. 

Jasmine. Jasmine is one of the most precious florals used ia perfumery. The concrete of jasmine is produced by hydrocarbon extraction of flowers from Jasminum officinale (var. GrandijJorum). The concrete is then converted to absolute by alcohoHc extraction. It is produced ia many countries, the most important of which is India, followed by Egypt. Jasmine products are rather expensive and are produced ia relatively small amounts compared with other materials. However, jasmine is particularly important ia perfume creation for its great power and aesthetic quaUties. Eour of the principal odor contributors to jasmine are OT-jasmone [488-10-8] (14), methyl jasmonate [91905-974-] (15), benzyl acetate [140-11 ], and iudole [120-72-9] (16). 

Orange Flower. Extraction of freshly picked flowers of the bitter orange tree, dims aurantium (subspecies amard) for the production of concrete is carried out mainly ia Morocco and Tunisia. Most of this material is processed further to give orange flower absolute, one of the most important absolutes used ia perfumes after rose and jasmine. It is highly valued ia perfumery, even when used at low levels, for its long-lasting, rich, warm, yet dehcate and fresh floralcy. The material is a complex mixture, to which methyl anthranilate [134-20-3] linalool (3), methyl jasmonate (15), and iadole (16) are important odor contributors. 

When the cyclic enone is unsubstituted, but the resulting enolate is quenched with an electrophile under conditions of kinetic control the irons adduct is formed exclusively303. Particularly successful is the sequential Michael addition/enolate alkylation in diastereoselective routes to frans-a,/j-difunctionalized cycloalkanones and lactones304-308. The key steps in the synthesis of methyl ( + )-jasmonate (3)309-310 (syn/anti diastereoselection) and (-)-khushimone (4) (syn/anti and induced diastereoselection) illustrate this sequence311 (see also Section D. 1.1.1.3.). 

In a related study the adduct of the lithium enolate of methyl bis(trimethylsilyl)acetale and ( —)-(/J)-2-(4-methylphenylsulfinyl)-2-cyclopentanone was transformed to ( — )-methyl jasmonate in > 99% ee. In contrast to the previous study described in this section, addition of the enolate proceeded apparently through a chelated form of the enone15. 

In this work, a suspension culture of Taxus chinensis, which produces a bioactive taxoid, taxuyunnanine C (Tc), was taken as a model plant cell system. Experiments on the timing of jasmonates addition and dose response indicated that day 7 and 100 pM was the optimal elicitation time and concentration for both cell growth and Tc accumulation [8]. ITie Tc accumulation was increased more in the presence of novel hydroxyl-containing jasmonates compared to that with methyl jasmonate (MJA) addition. For example, addition of 100 pM... 

Fig. 2. Time profiles of Tc content in T. chinensis suspension cultures elicited with methyl jasmonate (MJA), 2-Hydroxyethoxyethyl jasmonate (HEEJA), 2-hydroxyethyl jasmonate (HEJA), D-Glucosyl jasmonate (GJA) and 2,3-dihydroxypropyl jasmonate (DHPJA). One hundred pAf of each elicitor was added to the cultures in IpL of ethanol per ImL of culture medium on day 7 of cultivation. Data are the means of three flasks and vertical bars show standard deviations.

Ketchum, R.E.B., Rithner, C.D., Qiu, D. et al. (2003) Taxus metabolomics methyl jasmonate preferentially induces production of taxoids oxygenated at C-13 in Taxus x media cell cultures. Plant Metabolomics, 62, 901-909. 

Yukimune, Y., Tabata, H., Higashi, Y. and Hara, Y. (1996) Methyl jasmonate-induced overproduction of paclitaxel and baccatin III in Taxus cell suspension cultures. Nature Biotechnology, 14, 1129-1132. 

The industrially important cis-(+)-methyl jasmonate 119 is conveniently prepared by the hydrogenation of enone 120 with Me-DuPHOS and [Ru(l,2 5,6- ]-cod)( ]3 -methallyl)2.65°... 

Other assays have been used to evaluate the antioxidant activity against H202 of several plant-based products, namely, fruit juices from different cultivars of berries (Wang and Jiao 2000), fractions rich in phenolics isolated from the aqueous by-products obtained during the milling of oil palm fruits (Balasundram and others 2005), cherry laurel fruit and its concentrated juice (Liyana-Pathirana and others 2006), and strawberries and blackberries treated with methyl jasmonate, allyl isothiocyanate, essential oil of Melaleuca alternifolia, and ethanol (Chanjirakul and others 2007). 

Ayala-Zavala and others (2005) tested the effects of different natural antimicrobial volatiles (methyl jasmonate, ethanol, and their combination) on the phytochemical... 

It has been observed that treatment with natural antimicrobial volatiles also affected the antioxidant capacity of fruits (Ayala-Zavala and others 2005). ORAC values of control strawberries changed during storage at 7.5°C (Fig. 11.3, III). However, significant increases in antioxidant capacity values were observed in strawberries treated with methyl jasmonate, methyl jasmonate-ethanol, and ethanol. One explanation for this difference could be associated with differences on total phenol content (Ayala-Zavala and others 2005). 

Treatment of strawberry with methyl jasmonate resulted in a significant increase in total phenol content. However, even though antioxidant activity was the highest in those berries treated with methyl jasmonate, the combination methyl jasmonate-ethanol was the most effective in extending the shelf life. It appears that methyl jasmonate and ethanol treatments had an additive effect in maintaining quality of strawberries but not in retaining high antioxidant activity. 

Figure 11.3. Effect of natural product treatment (methyl jasmonate MJ 22 ptg/liter, ethanol ETOH 400 pl/liter, methyl jasmonate-ethanol (MJ-ETOH) on (I) total antho-cyanins (mg/100 g FW), (II) total phenols (mg/100 g FW), and (III) antioxidant capacity measured as ORAC (p.mol TE/g FW) of strawberry fruit (cv. Chandler) stored at 5°C. Bars show the final values after treatments. Different letters on top of the bars indicate statistical differences among treatments (p < 0.05).

Ayala-Zavala JF, Wang SY, Wang CY and Gonzalez-Aguilar GA. 2005. Methyl jasmonate in conjunction with ethanol treatment increases antioxidant capacity, volatile compounds and postharvest life of strawberry fruit. Eur Food Res Technol 221(6) 731-738. 

Gonzalez-Aguilar GA, Buta JG and Wang CY. 2001. Methyl jasmonate reduces chilling injury symptoms and enhances colour development of Kent mangoes. J Sci Food Agric 81 (13) 1244—1249. 

Yao HJ and Tian SP. 2005. Effects of biocontrol agent and methyl jasmonate on postharvest diseases of peach fruit and the possible mechanisms involved. J Appl Microbiol 98 941-950. 

PAULI, H.H., KUTCHAN, T.M., Molecular cloning and functional heterologous expression of two alleles encoding (5)-Y-methylcoclaurine 3 -hydroxylase (CYP80B1), a new methyl jasmonate-inducible cytochrome P-450-dependent monooxygenase of benzylisoquinoline alkaloid biosynthesis, Plant J., 1998,13, 793-801. 

Inomata100 utilized a tandem retro-Diels-Alder-ene reaction for an enantioselective total synthesis of (+)-methyl jasmonate (Scheme 41). The TMS group on the alkene was essential to the efficiency of the reaction, by producing a higher energy level of the HOMO for the ene reaction. 

---