Antifeedant natural products

In 1987, Vaultier and coworkers [27] developed a combination of a [4+2] cycloaddition of a bora-1,3-diene to provide an allylborane, which then reacts with an aldehyde to give a highly functionalized alcohol. The Lallemand group, as well as Hall and colleagues, has recently used this procedure. In an approach for the synthesis of the antifeedant natural product clerodin (4-83), Lallemand and coworkers performed a three-component domino reaction of 4-80, 4-81 and methyl acrylate to give 4-82 (Scheme 4.18) [28]. 

A SN reaction-based domino route to clerodane diterpenoid tanabalin (2-488) [258] has been described by Watanabe s group (Scheme 2.111) [259]. This natural product is interesting as it exhibits potent insect antifeedant activity against the pink bollworm, Pectinophora gossypiella, a severe pest of the cotton plant The domino sequence towards the substituted trans-decalin 2-487 as the key scaffold is induced by an intermolecular alkylation of the (5-ke toes ter 2-484 with the iodoalkane 2-483 followed by an intramolecular Michael addition/aldol condensation (Robin-... 

Panacene (61) is a metabolite of the sea hare Aplysia brasiliana and acts as a fish antifeedent [61]. The synthesis of the racemic natural product, published by Feldman et al. [77] in 1982, takes advantage of the anti-selective SN2 -substitution of the propargylic mesylate 67 with LiCuBr2 (Scheme 18.21). In contrast, the later attempted biomimetic synthesis by treatment of the enyne 68 with NBS or 2,4,4,6-tetrabromocyclohexadienone did not proceed stereoselectively and led to a 1 1 mixture of the target molecule 61 together with its allenic epimer [78]. 

Acetylnimbandiol was insectidical (EI50 = 21 ppm) when fed to the larvae of II. vlrescens, while the structurally related salannin, which lacks the A-ring ketone (Figure 13), was not (Table VII) (57). Nakanishi (58) has pointed out that natural products with electrophilic moieties tend to be cytotoxic and insect antifeedant. Possibly the growth-Inhibitory activity of the limonoids may also be attributed to a nonspecific electrophilic effect. 

Chimyl alcohol (Structure 7.79), isolated from the mantle tissues of the nudibranch Tritoniella belli,44 caused rejection by O. validus of shrimp-treated disks at natural tissue-level concentrations. T. belli sequesters this defensive chemistry from its diet, the stoloniferan coral Clavularia franklin-iana. Sequestration of chimyl alcohol from the diet, however, seems to be opportunistic, and T. belli also provisions its mucus with other yet undescribed deterrent natural products.49 Chimyl alcohol is reported from other non-Antarctic molluscs209 and has been demonstrated to function as an antibacterial and a fish antifeedant at levels found in the tissues of the dorid nudibranchs Archidoris montereyensis and Aldisa sanguinea cooperi.210... 

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