Pheromones, terpenoids

Together with the organoboron procedures mentioned above, the Pd-catalyzed cross coupling procedures have been applied to the synthesis of a wide variety of insect pheromones, terpenoids, and carotenoids. 

The faecal pellets of the bark beetle Ips paraconfusus which had fed on the phloem of Pinus ponderosa contained large quantities of the aggregation pheromones cis-verbenol (24), ipsenol (25), and ipsdienol (26). The pheromones originate in the hindgut, but, although there is a precursor-product correlation between a-pinene or myrcene from the phloem and the pheromone terpenoids, the biosynthetic site is unclear. The demonstration68 of the conversion of a-pinene into cis- and trans-verbenol (27) by Bacillus cereus found in the gut of I. paraconfusus has led to the... 

The western pine beetle Dendroctonus brevicomis is perhaps the most destmctive insect enemy of western pine forests. The aggregation pheromone is a mixture of the terpenoid myrcene [123-35-3J (163) from the tree and the frass pheromones exo-hsevicomki [20290-99-7] (164) and frontalin [28401-39-0] (165). The Norway spmce beede Ips tppopraphus converts the tree terpenoid myrcene into the frass pheromone ipsdienol [33628-00-3] (166) and the beedes also produce 2-methyl-3-buten-2-ol [115-18-4] and rir-verbenol [473-67-6] (167), all of which are components of the aggregation pheromone. 

Two illustrations that show the power of this reaction for the preparation of strained cycloalkenes are the contractions of 102 to the propellane 103 , an application that has been reviewed , and of 104 to the bicyclo[2.1.1]hexene 105 . The utility of the Ramberg-Backlund rearrangement in the preparation of various natural products such as steroids , terpenoids and pheromones has been demonstrated. In addition to the synthetic applications mentioned in the previous subsection, several selected examples taken from the recent literature are given in equations 66-69. These examples further demonstrate the potential of this method for alkene synthesis in general. 

The repertoire of chemicals that can be used for communication is limited by the biosynthetic ability of the insect. Compared to other insect orders, pheromone biosynthesis in Hymenoptera has received little study [191]. However, the biosynthetic origins of chemically diverse hymenopteran semiochemicals likely include aromatic, fatty acid, and terpenoid pathways as well as simple modifications of host-derived precursors. Notable recent studies include the biosynthesis of the fatty acid components (2 )-9-oxodec-2-enoic acid 52 and (2 )-9-hydroxydec-2-enoic acid of the honeybee queen mandibular pheromone from octadecanoic acid [192,193], and the aliphatic alcohol and ester... 

Terpenoid pheromones, 24 473 Terpenoid skeletons, 24 469 biosynthesis of, 24 471 Terpin hydrate, 3 231 a-Terpineol, 24 477, 509-512, 3 231 hydrogenation of, 24 512 a-Terpinyl acetate, 24 512 a-Terpinyl chlorides, 24 479 a-Terpinyl esters, 3 231 y-Terpinene, 3 230 Terpinolene, 24 493 Terpolymers... 

While the unbranched 204-207 clearly originate from the acetate pool, the structure of ( )-3,7-dimethyl-2-octene-l,8-dioic acid, callosobruchusic acid 207, a female produced copulation releasing pheromone of the azuki bean weevil, Callosobruchus chinensis [374] points to a terpenoid structure. The synthetic enantiomers [375] proved to be equally effective in releasing copulation behaviour in males. 

Snider and colleagues have developed the sequential ene reaction/thia-[2,3]-Wittig reaction which provide appropriately functionalized product 152 at allylic position on simple alkene 150 in two steps involving intermediate 151 (equation 87) . Thia-[2,3]-Wittig rearrangement was often utilized as a key step of natural product synthesis. Masaki and colleagues have demonstrated that the potassium enolate thia-[2,3]-rearrangement of aUyl sulfide 153 to 154 is useful for the synthesis of terpenoid diol component 155 of the pheromonal secretion of the queen butterfly (equation 88) . 

Pheromones are classified in at least ten different categories. The most conq)lex category involves enantiomers at a specific composition (Mori 2000), implying multiple receptors. Other complex networks of biological events involve terpenoids released by plants in response to grazing by herbivores. These metabolites can be used to attract parasitic wasps for pest control (Tumlinson 1993), or, like the strigolactones (Table 12.1), as useful germination stimulants of root parasites of plants in the families Scrophulariaceae and Orobanchaceae (Welzel 1999 Ryan 2001). 

In contrast to the rutelines, the melolonthine scarabs generally use terpenoid-and amino acid-derived pheromones (reviewed in Leal, 1999). For example, the female large black chafer, Holotrichia parallela Motschulsky, produces methyl (2.S, 3. Sj - 2 - am ino-3-methy lpcn tanoatc (L-isoleucine methyl ester) as an amino acid-derived sex pheromone (Leal et al., 1992 Leal, 1997). There is no direct evidence that the chafer beetles or any other Coleoptera use the shikimic acid pathway for de novo pheromone biosynthesis, but some scarabs and scolytids (see section 6.6.4.2) may convert amino acids such as tyrosine, phenylalanine, or tryptophan to aromatic pheromone components (Leal, 1997,1999). In another melolonthine species, the female grass grab beetle, Costelytra zealandica (White), the phenol sex pheromone is produced by symbiotic bacteria (Henzell and Lowe, 1970 Hoyt et al. 1971). 

The terpenoid-exocrine theme emphasized by scolytid beetles was again evident when the chemical constitution of the secondary attractant for the smaller European elm bark beetle, Scolytus multistriatus, was elucidated. The aggregation pheromone was identified as a mixture of (-)-4-methyl-3-heptanol, 2,4-dimethyl-5-ethyl-6,8-dioxabicyclo [3.2.1]octane (multistriatin) (XXII), and (-)-a-cubebene (XXIII), a host-derived synergist (70). All three compounds are required for the maximum attraction of beetles. The inactive diastereomers of 4-methyl-3-heptanol and multistriatin did not inhibit the responses of airborne beetles. 

Volatile isoprenoids that control insect behavior and development have been reviewed.476 Information on the biosynthesis of terpenoids with special emphasis on beetle pheromones has been compiled by Seybold and... 

Pheromones of insect species in the order Coleoptera are characterized by considerable structural diversity. Unlike the lepidopterous sex pheromones, which are nearly all tatty acid derivatives, coleopterous sex pheromone structures range in complexity from the relatively simple 3,5-tetradecadienoic acid of the black carpet beetle to the tricyclic terpenoid, lineatin, of the striped ambrosia beetle. While the sex pheromones of many beetles consist of mixtures of compounds that act synergistically to elicit a behavioral response, other Coleoptera species appear to use only a single compound for chemical communication between the sexes. In the latter case the compound usually has at least one chiral center and chirality plays a major role in determining pheromone specificity. 

Relatively few pheromones have been identified from species in this family. The first curcullonld pheromone Identified, that of the boll weevil, Anthonomus qrandls Boheman, is terpenoid in character like those of the Scolytidae. Two terpene alcohols (IX, X) and two aldehydes (xi, XII) were Isolated and identified from male weevils and from frass (21). All four of these compounds are required to elicit optimum attraction. 

S) -( — )-2-Methyl-2-hydroxy-y-butyrolactone (176a) is a useful synthon for the asymmetric construction of acyclic tertiary a-hydroxy acids found in natural products such as the pheromone frontalin and mevalonolactone, the biosynthetic precursor of terpenoids and steroids. This compound is readily prepared from lactone (175) using the asymmetric enolate oxidation protocol and dimethoxy oxaziridine ( + )-(158) <95JOC6l48>. The a-hydroxy lactone (176b), isolated as the benzoate, was obtained in 84% ee and 70% yield. A single crystallization from ethyl acetate improved the ee to >94% (Equation (41)). 

Since our last chapter was published, there has been only one Specialist Report on monoterpenoids, volumes 10 and 11 of this series lacking the monoterpenoid chapter there have been two subsequent reviews in the journal that replaces the Specialist Periodical Reports. An excellent compendium of naturally occurring monoterpenoids has been published, as well as a number of other reviews of a more specific nature, for example, on insect pheromones, on microbial transformations of terpenoid compounds, and on particular monoterpenoid skeletons, which are mentioned in the relevant sections of this chapter. The major publication that has appeared since our last chapter is the two-volume handbook of Erman this contains all the relevant literature up to about 1977 on monoterpenoids, including their synthesis. 

Terpenoids are a class of lipids displaying a great diversity of structures and functions, ranging from the small, volatile molecules in sex pheromones to the very large molecules in natural rubber.There is, however, a unifying theme, in that they are all formally constructed from C5 isoprene units, the number of which can be used to classify terpenoids (Table 2.5). 

The branched isoprene unit, which is also synthesized from the C, pool, is the basic structure of terpenoids. Less condensed structures are used as volatile pheromones, e.g., jasmonic acid, menthol, or camphor, or as natural rubber material. More condensed structures such as steroids and hopanoids are part of membranes, influencing their fluidity. They are also highly specific to their source organisms. Best known are cholesterol (in animals and plants), ergosterol (in fungi), and brassicasterol (in diatoms). Besides cellulose, hopanoids are the most abundant biomolecules. 

Sex pheromones are among the most widespread. Male moths can detect females by smell at a range of many miles. Some terpenoid pheromones are shown in Figure 1.9. Androst-16-en-3-ol is a porcine sex pheromone and the compound which produces boar taint in pork. 

Terpenes are known to play important ecological roles not only in the defense of the tree, but also in bark beetle chemical ecology. Two chapters in this volume (see chapters by Raffa, et al, and Tittiger, et al.) review aspects of terpenoids as chemicals in conifer-bark beetle interactions and isoprenoid formation in bark beetle chemical ecology. While some species of bark beetles may be able to produce monoterpene pheromones de novo, bark beetles can also use host-derived monoterpenes as precursors to their own sex and aggregation pheromones. Bark beetle monoterpene pheromones are often used in a stereospecific manner such that often only one enantiomer is able to serve as a sex or aggregation pheromone. Since both enantiomeric host-derived monoterpene precursors are accepted and chemically modified by the beetle, the exact monoterpene enantiomeric mixture of conifer resin is important to both the beetle s ability to produce the correct pheromone and to the trees ability to escape an attack. ... 

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