Terpenoid definition

Lipids are naturally occurring organic molecules that have limited solubility in water and can be isolated from organisms by extraction with nonpolar organic solvents. Fats, oils, waxes, many vitamins and hormones, and most nonprotein cell-meznbrane components are examples. Note that this definition differs from the sort used for carbohydrates and proteins in that lipids are defined by a physical property (solubility) rather than by structure. Of the many kinds of lipids, we ll be concerned in this chapter only with a few triacvlglycerols, eicosanoids, terpenoids, and steroids. 

The labelling studies described above provide definitive evidence for the mixed polyketide-terpenoid biogenesis of the andibenins, andilesins, andi-tomins, austin and terretonin. The formation of the bicyclo [2.2.2] octane system in the first two classes of metabolite provides a rare example of a biosynthetic Diels-Alder reaction. The biosynthetic relationship of austin and andibenin was supported by the isolation of austin from another mutant strain of A. variecolor [81]. Further metabolites related to austin have been isolated from Emericella dentata [82] and Penicillium diversum [81]. Other complex metabolites which are almost certainly further products of the meroterpenoid pathway are fumiga-tonin (102) and paraherquonin (103) which have been isolated from Aspergillus... 

Interest in enzyme stereospecificity and the stereochemistry of prochiral centres, such as the methylene groups of mevalonic acid, has necessitated more precise definitions of the stereochemistry of the various molecules involved and of the enzymological consequences. The use of multiply labelled mevalonic acid in terpenoid and steroid biosynthesis has been reviewed by Hanson. The Proceedings of the 1970 Phytochemical Society symposium have been published. They include a general discussion of terpenoid pathways of biosynthesis by Clayton and specific chapters on monoterpenoids, diterpenoids, eedysones, carotenoids, isoprenoid quinones, and chromanols. Other reviews concerning biosynthesis have appeared on furanocoumarins, indole alkaloids, monoterpenoids, and diterpenoids. ... 

The terpenoid indole alkaloids are a group of plant bases derived by multiple variation on the strictosidine [(79) p. 20] skeleton. Arguably the most important work in the past five years has been done on these alkaloids with enzyme preparations from plant tissue cultures, and the research is of great potential significance for other studies in alkaloid biosynthesis. The results have allowed close definition of the early stages of biosynthesis (this Report, p. 19). Use of crude enzyme preparations in this way has been extended to the study of benzylisoquinoline biosynthesis, with enzyme-catalysed formation of norlaudanosoline-1-carboxylic acid [(57) p. 16] this compound had earlier been identified as the first of the benzylisoquinolines (this Report, p. 15). It seems that amino-acids of this general formula (6) are key intermediates in the biosynthesis of all isoquinoline alkaloids. Lophocereine (7) is exceptional in that two routes (from leucine and mevalonate) may lead to it, only one of which potentially involves an acid like (6). ... 

Typical alkaloids are alkaline organic componnds containing one or more nitrogen atoms, each connected to at least two carbon atoms within a heterocyclic ring system. They have limited distribntion in plants, so that vitamins and hormones are exclnded even thongh they may strnctnrally comply with the definition. Most alkaloids are derived at least partly from varions amino acids as their direct precnrsors, while a few are derived from isoprene nnits (terpenoids). 

At the present time there would seem no definitely proven example of a terpenoid serving as an oviposition lure, but recently it was shown [709] that the triterpenoid cucurbitacins act as feeding attractants to phytophagous insects attacking plants of the Cucurbitaceae, which suggests that other higher terpenoids may also be found to possess this hitherto unsuspected activity. 

The term terpene is used to describe a compound, which is a constituent of an essential oil containing carbon and hydrogen or carbon atoms, hydrogen, and oxygen atoms, and is not aromatic in character [24, 25]. This definition is usually extended to include other compounds called terpenoids, which are not of natural occurrence but are very closely related to the natural terpenes. Most terpenes, which include terpenoids, are invariably hydrocarbons, alcohols, aldehydes, ketones, or oxides, and they may be solids or liquids. Terpene hydrocarbons are usually liquids, while terpenes of higher molecular weights, mostly obtained from the natural gums and resins of plants and trees, are not steam volatile. 

Hemiterpenes, by definition, consist of only one isopentane unit and are, thus, the simplest members of terpenoids. The basic building blocks of isoprenoids, namely IPP and DMAPP, must be universally present in green plants, being the progenitors of the phytyl side chain of chlorophyll, which is essential for biological activity (Sect. 8.1.4). These do not appear to be accumulated by plants (3), though the related prenyl alcohol (3,3-dimethylallyl alcohol, 9) and its isomer isoprene alcohol (10) have been found to occur in a few essential oils (229). Isoprene (11) itself is an important emittant of pine forests (165). 

Terpenoids can be analyzed by the usual methods. For the volatile members of the family, gas chromatography-mass spectrometry (gc-ms) is a particularly useful tool. In laboratories (e.g., those in the major fragrance companies), which are accustomed to analyzing mixtures of volatile terpenoids, gc-ms is the major analytical technique employed and such laboratories will have extensive libraries of mass spectra of terpenoids to assist in this. However, the mass spectral fragmentation patterns of closely related terpenoids are often so similar as to render definitive identification by ms alone, impossible. For these materials and those for which there is no reference (e.g., compounds newly isolated from nature), nuclear magnetic resonance (nmr) spectroscopy is the analytical tool of choice. Physical techniques, e.g., density, refractive index, and optical rotation, are relatively inexpensive and prove useful in quality control. 

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