Terpenoids, homologation

Gas chromatography (GC or, less commonly, GLC) is the most widely used separation technique for volatile samples. The resolution is sufficient to routinely separate components, such as homologous series, saturated from unsaturated fatty acids, terpenoids, triacylglycerols, etc. The use of a mass spectrometer to identify the separated components (GC-MS) is discussed in Section 8.4. 

Many natural products, i.e. homologous aliphatic (lipids), polar (sugars, amino acids), and cyclic (terpenoids) compounds can be utilized as biomarkers. The following is a brief overview of the classical biomarkers commonly used, namely lipids and terpenoids. 

SCHEME 70. Iterative one-pot homologation of terpenoids containing 1,5-diene units with ( )-and (Z)-l,4-diiodo-2-methyl-l-butenes and its application to the synthesis of coenzyme Qs, famesol, and geranylgeraniols171... 

Raney nickel reduction yields a homologous series of bicyclic terpenoid hydrocarbons of basic structure... 

Reports are available on the discovery of insect anti-feeding substances and anti-juvenile hormones, on the homology of biosynthetic routes and its basis in chemotaxonomy, and on the role of terpenoids in chemical ecology. Further speculations have been made about the biosynthesis of various classes of sesquiterpenoid based on the results of a study of the quantitative co-occurrence of these in the genus Hymenaea. 

The biosynthesis of sesquiterpenes in plants appears to be isolated from that of either monoterpenes or diterpenes. A prenyl transferase isolated from pumpkin Cucurbita pepo, Cucurbitaceae) converts C5 units into FPP, but not into gera-nylgeranyl pyrophosphate (the precursor to diterpenes). Another enzyme from the same source forms C20 terpenoids from C5 units, but does not accumulate lower homologs (also see Chapters 19 and 22). However, because famesyl pyrophosphate synthetase is a branch-point metabolite for the synthesis of sesquiterpenes, triterpenes, and sterols, this enzyme is ubiquitous in plants (Croteau and Johnson, 1985). 

Despite great diversity in form and function, the terpenoids are unified in their common biosynthetic origin. The biosynthesis of all terpenoids from simple, primary metabolites can be divided into four overall steps (a) synthesis of the fundamental precursor IPP (b) repetitive additions of IPP to form a series of prenyl diphosphate homologs, which serve as the immediate precursors of the different classes of terpenoids (c) elaboration of these allylic prenyl diphosphates by specific terpenoid synthases to yield terpenoid skeletons and (d) secondary enzymatic modifications to the skeletons (largely redox reactions) to give rise to the functional properties and great chemical diversity of this family of natural products. As bacosides are triterpenoid derivatives, they may probably foUow the common biosynthetic pathway of terpenoid production [40]. 

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