Cis- Jasmone

Fragrances Jasmone Cis cA-3-Methyl-3- (2-pentenyl) -2-cyclopenten-l-one Givaudan, Switzerland... 

Isoamyl 4-(2-furan) butyrate Methyl jasmonate cis-Methyl jasmonate Nonenyl succinic anhydride Octyl 2-furoate C13H20O4... 

Cis-Jasmone (TM 422) is an important ingredient inmany perfumes. There are several obvious disconnections and it may help you to know that cychsation of the diketone 422A does indeed selectively give cis-jasmone. 

Fourteen syntheses of cis-jasmone are given in chart from in Natural Products Chemistry ed. K.Nakanishi et. ah. Academic Press, New York, 1975, vol.2, p.21. 

Jacobson-Hugershofi synthesis benzothiazoles, 5, 135 Japp-KJingemann reaction JV-arylhydrazones from, 4, 337 1,2,4-triazole synthesis by, 5, 768 Jasmine lactone synthesis, 3, 847 Jasminine occurrence, 2, 626 y-Jasmolactone synthesis, 4, 674 cis-Jasmone synthesis, 1, 422, 427 Jatropham synthesis, 1, 426 Josephson junctions, 1, 359 Juliprospine... 

In the reaction of a-sulfonyl carbanion with lactones, the corresponding hydroxy-co-ketosulfones were obtained " . Thus, various o-hydroxyketones were shown by Umani-Ronchi and coworkers to be formed from the corresponding lactones. For example, the reaction of a, a-dilithioalkyl phenyl sulfones with lactones in THF at low temperatures afforded co-hydroxy-jS-ketosulfones which, upon desulfonylation with aluminium amalgam, gave the corresponding hydroxyketones . This process was applied for the syntheses of cis-jasmone and dihydrojasmone by treating y-valerolactone with ds-3-hexen-l-yl phenyl sulfone and n-hexyl phenyl sulfone. ... 

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°... 

The alcohol moiety is produced in a different manner from that of the acid moiety. The alcohol moiety resembles the plant hormone jasmonic acid (JA) (26) generated from linolenoyl moiety of lipids via (13,S )-hydroperoxy-linolenic acid (22), (12.13,S )-epoxylinolenic acid (23), and 12-oxo-cis-10.15-phytodienoic acid (24) by the oxylipin or octadecanoid pathway (Fig. 3) [31]. In fact, 13C was incorporated at pyrethrolone (1) carbon positions that agreed with those predicted to be labeled when the alcohol moiety is produced via the pathway (Fig. 3) [30]. Figure 3 illustrates that m-jasmone (25) is hydroxylated to yield jasmololone (4), which is then dehydrogenated to yield pyrethrolone (5). However, it has not yet been determined if this is actually the case. 

In fact a 1,4-dissonant system may be also reconnected to a dissonant 5-membered heterocycle. This solution is also valid when the heterocycle is an easily available starting material such as furan or furfural. For instance, syntheses of cis-jasmone (3) have been reported which follow retrosynthetic schemes shown in Scheme 5.24 [27] ... 

Draw the structures of the bicyclo[3.1.0]hex-2-ene-2-carboxaldehyde, cis-jasmone, the Wieland-Miescher ketone and the bis-nor-analogue -which you may find through the "Subject index"- and ... 

Bruce TJA, Matthes MC, Chamberlain K, Woodcock CM, Mohib A, Webster B, Smart LE, Birkett MA, Pickett JA, Napier JA (2008) cis-Jasmone induces Arabidopsis genes that affect the chemical ecology of multitrophic interactions with aphids and their parasitoids. Proc Natl Acad Sci USA 105 4553 558... 

Diketones are readily transformed to cyclic derivatives, such as cyclopentanones and furans. In this manner, the fragrance dihydrojasmone (3-methyl-2-pentyl-2-cyclopenten-l-one) is prepared by the base-catalyzed aldol condensation of 2,5-undecanedione. 2,5-Undecanedione is itself prepared from heptanal and methyl vinyl ketone in the presence of thiazolium salts (329). cis-jasmone can be similarly prepared (330,331). 

The jasmonates are another class of disubstituted cyclopentanoid natural products very reminiscent of the prostaglandins. To efficiently assemble their main skeleton, Yamamoto and co-workers developed a clever three-component reaction methodology that was demonstrated by the total synthesis of both trans- and cis-methyl jasmonates 36 and 37 (Scheme 12.7) [25],... 

An unsymmetrical example is the allylic halide 19 needed for the synthesis of cis jasmone. Obvious disconnections take us back to 21 and a simple three-component synthesis. 

As the alcohol 22 was available it was simply a case of putting in the ethyl group. Of course the alternative order of events might be better. Since the reduction to the ds-alkene can be done either before or after incorporation into the cis-jasmone skeleton, 22 was also transformed5 into the propargylic bromide 24. 

In fact, the diketone 49 was not isolated but was cyclised with dilute aqueous base to give cis-jasmone 52 in excellent yield. We shall be exploring reactions of this sort in chapters 18-28. 

The accessibility to 2,3-disubstituted — and 4,5-disubstituted 2-cyclopentanones by this thermal C3 -< C5 ring expansion has been illustrated by the syntheses of dihydrojasmone 92), cis-Jasmone 92) and dicranenone A188). 

Enol ethers react with diazo ketones in the presence of Cu-catalysts to give cyclopropanes such as 24. Ring cleavage with acid and subsequent intramolecular aldol condensation constitutes a flexible route to cyclopentenones (Eq. 7) 12-13). This procedure has also been applied to a synthesis of cis-jasmone employing isopropenyl acetate as a donor olefin 14). 

Plants utilize methyljasmonate not only for floral scent but also as a cellular regulator that controls a myriad of plant functions.76 The cis epimer (Fig. 11.3) is believed to be the most biologically active.77 Like methylsalicylate, methyljasmonate and its precursor jasmonic acid have been implicated in the induction of defense-related genes in plants that are damaged by herbivores or challenged by infection.78,79 Application of methyljasmonate either directly to the plant or in a volatilized spray can induce the expression of known pathogenesis-related proteins.80 82... 

Formation of the cyclopentane ring and concomitant arrangement of the two side chains in the cis fashion is another efficient approach to methyl < />/-jasmon ate as delineated in Scheme 9. In the upper sequence, nickel-catalyzed carbozincation of 17 with Et2Zn produced organozinc 18, which was converted to a copper reagent for coupling with 1-bromoacetylene to produce 19 efficiently.849 The ene reaction of 20 and 23 has afforded 21 and 24, respectively.858 859 In the latter case, 23 was generated in situ by retro Diels-Alder reaction of 22. 

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