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Formation of Unsaturated Products
Lecanoric acid, empirical formula C16H14O7, is an ester formed from the condensation of two
molecules of orsellinic acid Ô.
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Èethylation

Decarboxylation

Reduction

Oxidation
Èethylation

  

 

1. Ketone reduction followed by dehydration is often used as a


method for introducing a double bond (in the biosynthesis of
unsaturated fatty acids).
2. The alkene  is in fact biosynthesized from the polyketide . Propose
a reasonable synthesis of compound  from polyketide  which does
not involve the polyketide  as an intermediate.
  
1. One common biosynthetic oxidation is the conversion of a methyl group which
is directly attached to a benzene ring into its corresponding carboxylic acid 
Dr-CH3 > DrCO2H.
2. D second type of oxidation process which is commonly encountered in
biosynthesis is  $  of benzene rings giving the corresponding phenol
derivatives  Dr-H > Dr-OH (Dr = benzene ring). These reactions are catalysed
by enzymes known as $

(so-called because they introduced
one oxygen atom from oxygen) and there is little precedence for similar
reactions in organic chemistry.
3. 1,4-Dihydroxybenzene  derivatives can be oxidised to their corresponding
r
 (quinones are cyclic dicarbonyl compounds in which the carbonyl
groups are linked by carbon-carbon double bonds) by enzymes known as
  

(Figure 18). Two hydrogen atoms are removed in going from
compound  to compound , hence the name dehydrogenase. Compounds
such as  are often used in organic chemistry as dehydrogenation agents
because they can readily accept two hydrogen atoms. Related dihydroxy-
compounds, such as compound  similarly can give quinones  .

Figure 21 shows the biosynthesis of the pigment, hypericin  from the


precursor Ô. Three phenoxy radical dimerisations and one quinone forming
oxidation are involved in this biosynthesis.
   ð  

1. In the biosynthetic reactions we have discussed so far,


acetyl coenzyme D has always been used as the starter unit
for polyketides. Other starter units can also be used and this
increases the structural diversity of polyketide-derived
natural products. Two examples of other starter units are
benzoyl coenzyme D  and cinnamoyl coenzyme D 

2. Two examples of how the novel starter units  and  are


used in biosynthesis are shown in Figures 23 and 24
respectively.

3. Flavanones and related compounds (Figure 24) are


responsible for the colours in higher plants.
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Polyketide pathway is used to produce phenolic materials and their
derivatives. Not all phenolic materials are biosynthesized from
polyketides however, some products are derived from shikimic acid  in
a process termed the shikimic acid pathway.
1,3-Dicarbonyls:Keto-Enol Tautomerism
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