Phenylpropanoid biosynthesis pathway

Phenylpropanoid Biosynthesis in Plants Enzymology and Pathway Topology 491 Transcriptional and Posttranscriptional Regulation of Phenylpropanoid Biosynthesis in Plants 504... 

Phenylpropanoid Biosynthesis in Plants Enzymology and Pathway Topology... 

In either of the proposed pathways, salicylic acid is synthesised from tram-cinnamic acid. This is an intriguing observation and may provide a clue as to how and why the induction of SAR is tightly linked to the formation of a necrotic lesion. When plants react hypersensitively to pathogen attack, many biochemical changes occur, including the induction of phenylpropanoid biosynthesis. In bean, as well as other plants, this induction seems to be at least partly caused by an increase in the synthesis of phenylalanine ammonium lyase and other enzymes involved in the biosynthesis of isoflavonoid phytoalexins, flavonoid pigments and... 

The understanding of the degradation of natural products such as camphor has been greatly enhanced by understanding the catalytic cycle of the cytochrome P-450 enzyme P-450cam in structural detail.3,4 These enzymes catalyze the addition of 02 to nonactivated hydrocarbons at room temperatures and pressures - a reaction that requires high temperature to proceed in the absence of a catalyst. O-Methyltransferases are central to the secondary metabolic pathway of phenylpropanoid biosynthesis. The structural basis of the diverse substrate specificities of such enzymes has been studied by solving the crystal structures of chalcone O-methyltransferase and isoflavone O-methyltransferase complexed with the reaction products.5 Structures of these and other enzymes are obviously important for the development of biomimetic and thus environmentally more friendly approaches to natural product synthesis. 

The biosynthesis of the stilbenoids, including 1, has been previously reviewed. Briefly, the synthesis of 1 is dependent upon a single key enzyme known as stilbene synthase or resveratrol synthase as part of a mixed phenylpropanoid-polyketide pathway [2,3,4,5,6] (Fig. (1)). Stilbene synthase catalyzes the formation of 1 through the condensation of one p-coumaroyl CoA and three malonyl CoA molecules, both of which are ubiquitous intermediary plant metabolites. 

The analysis of mutants of the phenylpropanoid pathway in Arabidopsis, as outlined in this review, has led to numerous revisions of the pathway over the past decade. The presently accepted pathway clarifies some of the contradictory data of the past, but also poses new questions for which we do not yet have answers. For example, a growing body of evidence suggests that neither ferulic acid nor sinapic acid are intermediates in phenylpropanoid biosynthesis. This is problematic in that many plant cell walls contain esterified ferulic acid, " and sinapic acid esters are major soluble secondary metabolites in Arabidopsis leaves and seeds. If the most current model of the pathway is correct, how are these molecules synthesized ... 

Fig. 10. The pathway of aromatic biosynthesis in the cytosol and its point of interface with phenylpropanoid biosynthesis at the reaction catalyzed by phenylalanine ammonia-lyase (PAL). Enzymes sensitive to inhibition by caffeic acid (CAF) are indicated by dark shading. Abbreviations as in Figure 9 additionally, GIN, cinnamic acid COU, coumaric acid.

Many plants utilize different PAL isoforms for stress responses or for biosynthesis of structural components, and these different PALs exhibit differential expression in distinct tissues. Metabolic channeling may help control the flux of phenylalanine through PAL into the different phenylpropanoid branch pathways [6,7]. 

Resveratrol biosynthesis branches from the phenylpropanoid pathway. The resveratrol biosynthesis pathway consists of four enzymesrphenylalanine ammonia lyase (PAL), cinnamic acid 4-hydroxylase (C4H), 4-coumarate CoA ligase (4CL), and stilbene synthase (STS). The first two enzymes of the pathway, PAL and C4H, convert phenylalanine into /)-coumaric acid. The third enzyme, 4CL, attaches /)-coumaric acid to the pantetheine group of coenzyme-A (CoA) to produce 4-coumaroyl-CoA. The fourth enzyme, STS, catalyzes the condensation of resveratrol from one molecule of 4-coumaroyl-CoA and three molecules of malonyl-CoA, which originate from fatty acid biosynthesis. TAL is homologous to PAL and converts the amino acid tyrosine directly into / -coumaric acid. Methylated resveratrol derivatives of pinostilbene and pterostilbene are produced by resveratrol O-methyltransferase (ROMT) from resveratrol [135] (Figure 10.10). 

The earliest references to cinnamic acid, cinnamaldehyde, and cinnamyl alcohol are associated with thek isolation and identification as odor-producing constituents in a variety of botanical extracts. It is now generally accepted that the aromatic amino acid L-phenylalanine [63-91-2] a primary end product of the Shikimic Acid Pathway, is the precursor for the biosynthesis of these phenylpropanoids in higher plants (1,2). 

Plant metabolism can be separated into primary pathways that are found in all cells and deal with manipulating a uniform group of basic compounds, and secondary pathways that occur in specialized cells and produce a wide variety of unique compounds. The primary pathways deal with the metabolism of carbohydrates, lipids, proteins, and nucleic acids and act through the many-step reactions of glycolysis, the tricarboxylic acid cycle, the pentose phosphate shunt, and lipid, protein, and nucleic acid biosynthesis. In contrast, the secondary metabolites (e.g., terpenes, alkaloids, phenylpropanoids, lignin, flavonoids, coumarins, and related compounds) are produced by the shikimic, malonic, and mevalonic acid pathways, and the methylerythritol phosphate pathway (Fig. 3.1). This chapter concentrates on the synthesis and metabolism of phenolic compounds and on how the activities of these pathways and the compounds produced affect product quality. 

Ring B and the central three-carbon bridge forming the C ring (see Fig. 5.1) originate from the amino acid phenylalanine, itself a product of the shikimate pathway, a plastid-based process which generates aromatic amino acids from simple carbohydrate building blocks. Phenylalanine, and to a lesser extent tyrosine, are then fed into flavonoid biosynthesis via phenylpropanoid (C6-C3) metabolism (see Fig. 5.1). 

Validation of the role of femloyl-CoA in the synthesis of the vanillin precursor will be detection of the appropriate intermediates and/or enzyme activities in placental extracts that could account for the production of the predicted levels of capsaicinoids. The presence of low levels of monolignol intermediates could be explained by lignin biosynthesis. An alternate route from phenylalanine to vanillin has been considered by some investigators Orlova et al. [68] demonstrated the role of the benzenoid pathway in petunia flowers for the biosynthesis of phenylpropanoid/benzenoid volatiles. 

---