Naturally occurring precursors structure

Inhomogeneity is quite naturally predicted to occur in this class of complexes. This is not only due to the different possible breakdown pathways in soils, sediments, etc., but is also due to the multiplicities of naturally occurring precursors in living organisms. For example, a number of known chlorophyll structures are shown in (23). The structural complexity is even more elaborate for the haems. Mixtures in geological media thus are to be expected. However, it should be pointed out that the amount of porphyrins from plant sources is overwhelming compared to that... 

In summary, model studies are very efficient for the identification and structure elucidation of important flavor components. Most of the compounds reported here have not been identified in meat and have not yet been reported as constituents of food volatiles. Nevertheless, there are good reasons to believe that minute traces of these sulfur-containing components are present in roasted and/or cooked meat volatiles because our model system was based solely on naturally occurring precursors. We believe that only minute trace amounts of these types of components need to be present in natural products to be of prime significance due to their extremely low odor threshold values. 

In the Chapter 6 Focus On, "Terpenes Naturally Occurring Alkenes," we looked briefly at terpenoids, a vast and diverse group of lipids found in all living organisms. Despite their apparent structural differences, all terpenoids are related. All contain a multiple of five carbons and are derived biosynthetically from the five-carbon precursor isopentenyl diphosphate (Figure 27.6). Note that formally, a... 

Subsequent cyclizations, dehydrogenations, oxidations, etc., lead to the individual naturally occurring carotenoids, but little is known about the biochemistry of the many interesting final structural modifications that give rise to the hundreds of diverse natural carotenoids. The carotenoids are isoprenoid compounds and are biosynthesised by a branch of the great isoprenoid pathway from the basic C5-terpenoid precursor, isopentenyl diphosphate (IPP). The entire biosynthesis takes place in the chloroplasts (in green tissues) or chromoplasts (in yellow to red tissues). 

In contrast to other 2,5-anhydroaldoses (which exhibit mutarota-tion, possibly due to the formation of hemiacetals28), 2,5-anhydro-D-glucose does not show any mutarotation.27 The importance of this compound as a potentially useful precursor to C-nucleosides warrants a reinvestigation of the deamination reaction, and the definitive proof of the structure of the compound. The readily accessible 2,5-anhydro-D-mannose (11) does not possess the cis-disposed side-chains at C-2 and C-5 that would be required of a synthetic precursor to the naturally occurring C-nucleosides, with the exception of a-pyrazomycin (8). The possibility of an inversion of the orientation of the aldehyde group in 11 by equilibration under basic conditions could be considered. 

Currently we know very little about naturally occurring tetrodotoxin analogs or precursors. Chiriquitoxin, isolated along with tetrodotoxin from the Costa Rican frog Atelopus chiriquiensis (21,22), is known to possess the same basic skeleton as tetrodotoxin but differs by an uncharacterized substituent at C-6, as shown in the structure below. It also was shown, based on isolation experiments, that... 

Biogenetic pathways leading to naturally occurring pyrrolizidine bases were proposed by Robinson, Schopf, and Lukefi (see, e.g., refs. 119-121) in their publications concerned with the biogenesis of alkaloids. The most probable precursors of the pyrrolizidine system are commonly accepted to be ornithine (176), hydroxyomithine (177), and their biogenetic equivalents. It is noteworthy that ( + )- -hydroxy-jV-methylnorvaline (178) (structurally related to ornithine) was isolated... 

The parent nucleus of the flavonoids is flavone ((58), 2-phenylchromone or 2-phenylbenzopyran-4-one). Flavone and isoflavone ((59), 3-phenylchromone, the parent nucleus of the isoflavonoids) are the simplest oxygen-containing naturally occurring compounds that possess the 2-phenylnaphthalene -type structure. The chalcones, represented by the nucleus (60), may be regarded as open-chain flavonoids and are usually hydroxylated. The interconversion of chalcone and flavonone catalyzed by chalcone isomerase is well known [326, 327, 331], Chalcones can be precursors of both the flavonoids and the isoflavonoids [326-332]. 

Many natural products display structural motifs biosynthetically derived from ortho-quinol precursors, and some even feature ortho-quinol moieties in their final structural arrangement [1, 6]. Asatone (7) and related neolignans can be put forward as classic examples of complex natural products derived from cyclodimerization of oxidatively activated simple phenol precursors (Figure 5) biomimetic syntheses of 7 have accordingly been accomplished by anodic oxidation (Section 15.2.1) and by Pelter oxidation (Section 15.2.2) of the naturally occurring phenol 9 [34, 36]. 

The two-dimensional structures are extended networks formed by the linking of the metal-oxygen polyhedra and the phosphate tetrahedra. These are sheet structures and often resemble those of naturally occurring clay minerals. The sheets are usually anionic and the protonated (cationic) amine molecules, located between the two sheets, render the framework neutral. The two-dimensional structures are intermediates between the one-dimensional chains and the three-dimensional structures, and the literature on phosphate networks contains descriptions of several layered materials, owing to the wide compositional diversity exhibited by them [22-24]. The layered materials are of interest because they act as precursors for the three-dimensional structures. 

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