Shikimic acid dehydrogenase

Because of the lack of shikimic acid dehydrogenase, 3-dehydroshikimic acid accumulates. Catechol-0-methyltransferase is not very selective. Apart from methylation in the meta-position, the para-hydroxy group is also methylated to an extent of ca. 20 mole%. The addition of methionine increases significantly the vanillic acid content in the product mixture. 

L-Phenylalanine,which is derived via the shikimic acid pathway,is an important precursor for aromatic aroma components. This amino acid can be transformed into phe-nylpyruvate by transamination and by subsequent decarboxylation to 2-phenylacetyl-CoA in an analogous reaction as discussed for leucine and valine. 2-Phenylacetyl-CoA is converted into esters of a variety of alcohols or reduced to 2-phenylethanol and transformed into 2-phenyl-ethyl esters. The end products of phenylalanine catabolism are fumaric acid and acetoacetate which are further metabolized by the TCA-cycle. Phenylalanine ammonia lyase converts the amino acid into cinnamic acid, the key intermediate of phenylpropanoid metabolism. By a series of enzymes (cinnamate-4-hydroxylase, p-coumarate 3-hydroxylase, catechol O-methyltransferase and ferulate 5-hydroxylase) cinnamic acid is transformed into p-couma-ric-, caffeic-, ferulic-, 5-hydroxyferulic- and sinapic acids,which act as precursors for flavor components and are important intermediates in the biosynthesis of fla-vonoides, lignins, etc. Reduction of cinnamic acids to aldehydes and alcohols by cinnamoyl-CoA NADPH-oxido-reductase and cinnamoyl-alcohol-dehydrogenase form important flavor compounds such as cinnamic aldehyde, cin-namyl alcohol and esters. Further reduction of cinnamyl alcohols lead to propenyl- and allylphenols such as... 

In this process, sugars, obtained from biomass, are fermented at low pH into cis-muconic acid. The process of microbial muconic adic formation was already described by Frost and coworkers, who developed E. coli WNl/pWN2.248 that synthesized 36.8 g/L of c/s,ci>muconic acid in 22% (mol/mol) yield from glucose after 48 h of culturing under fed-batch fermentation conditions [147]. This strain did not possess the aroE encoded shikamate dehydrogenase preventing the cells to convert 3-dehydroshikimic acid into shikimic acid which is available for production of cis,cis-muconic acid. Optimization of microbial cis.m-muconic acid synthesis required expression of three enzymes not typically found in E. coli. A recent patent application by Bui et al. describes a productivity of 59 g/L cis muconic acid from 248 g/L glucose by a modified E. coli. in a 20 L fermenter in 88 h. 

Quinic acid is also found throughout the plant kingdom, usually with shikimic acid. It occurs as the free acid in many plants and its phenolic esters are also very common. The simplest assumption for the biosynthesis of quinic acid is through the reduction of 3-dehydroquinic acid, catalyzed by quinate dehydrogenase. However, because of the rare occurrence of this enzyme, the biosynthesis of quinic acid still remains to be explained. 

Figure 4 Current view of the phenylpropanoid pathway to the monolignols 19-23. 4CL, 4-hydroxycinnamate coenzyme Aligases pC3H , p-coumarate 3-hydroxylase C4H, cinnamate 4-hydroxylase CAD, cinnamyl alcohol dehydrogenases CCOMT, hydroxycinnamoyl CoA O-methyltransferases CCR, cinnamoyl-CoA oxidoreductases COMT, caffeic acid O-methyltransferases F5H , ferulate 5-hydroxylase HCT, hydroxycinnamoyl-CoA shikimate hydroxycinnamoyltransferase HOT, hydroxycinnamoyl-CoA quinate hydroxycinnamoyltransferase PAL, phenylalanine ammonia lyase TAL, tyrosine ammonia lyase.

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