CHEMISTRY OF NATURAL PRODUCTS ppt

CHEMISTRY OF NATURAL PRODUCTS
CHEMISTRY OF NATURAL PRODUCTS
(professor Manolis Stratakis)
Overview
1. Biosynthesis of terpenes
2. Biosynthesis of phenols
3. Metabolism of fatty acids
4. Metabolism of glucose (glycolysis)
5. Anabolic pathways of fatty acids
and carbohydrates
Biosynthesis of acyclic terpenoids
OPP
Me
Me OPP
Me
CH
3
COSCoA
Claisen-type
condensation
CH
3
COCH
2
COSCoA
Aldol-type
condensation
2 NADPH 2 NADP
3 ATP
3 ADP
Me

OP
O
HO OPP
CO
2
, Pi
Isomerization
Terpenes
From the metabolic pathways
of carbohydrates and fats
Isoprene units
Condensation of isoprene units. Formation of acyclic
terpenes
OPP
OPP
H
OPP
OPP
-H
+
geranyl OPP
OPP
farnesyl OPP
squalene
OPP
tail-tail dimerization
OPP
geranylgeranyl OPP
OPP
Formation of monoterpenes (examples)

Me Me
Me
OPP
Me Me
Me
OPP
- OPP
Me
Me Me
α-terpinyl cation
Me
Me
Me
OH
Me Me
Me
Me
O
Me
limonene
fenchone
camphene
3-carene
geraniol
myrcene
Me
Me
Me
Me
Me

Me
Me
CH
2
Me
Me
α- and β-pinene
enzyme
Formation of sesquiterpenes (examples)
Me Me
Me Me
OPP
Me Me
Me
Me
Me
Me
Me
Me
H
H
Me
Me
Me
Me
OH
bisabolene
cadinene
carotol
Formation of diterpenes (examples)

Me Me
Me Me Me
OPP
geranylgeranyl-OPP
Me
Me
Me
kaurene
Me
Me
Me
Me
pimaradiene
Me
Me
Me
labdadienol
OH
Me
Biosynthesis of squalene
Me Me
Me Me
farnesyl-OPP
OPP
MeMe
MeMe
PPO
Enz-Nu
-Enz-Nu
Me Me

Me Me
MeMe
Me
PPO
Me
Me Me
Me Me
MeMe
Me
Me
NADPH
squalene
Me
Me Me Me
Me
Me
Me
Me
Biogenesis of steroids and triterpene alcohols (examples)
squalene
Me
Me Me Me
Me
Me
Me
Me
O
H
+
HO

Me
Me
Me
Me
HO
Me
Me
H H
Me
H
Me Me
Me
H
Me Me
Me
H
2,3-epoxysqualene
epoxidation
Me
Me Me
Me
H
H
H
HO
Me
Me
Lanosterol
Me
Me

- H
Cholesterol
Biogenesis of phenols through polyketides
CH
3
COSCoA
Claisen-type
condensation
CH
3
COCH
2
COSEnz
itteration
Me S
O
CoA
OOO
1
7
2
6
Aldol C2-C7
O
O
OH
Me
SCoA
O
-H

2
O
Me
OH
HO
COOH
hydrolysis
orsenilic acid
Aldol C6-C1
Me
O
O
O
O
Me
O
OH
OH
HO
floroacetophenone
polyketide
Biogenesis of phenols: other examples
HOOCCH
2
COSEnz
Me
S
O
CoA
OO

Aldol
O
O
OH
Me
-CO
2
O O
OH
Me
O
Senz
OMe
O
Senz
Me
COOH
OH
salicylic acid
S
O
CoA
OO
O
O
Me
Me
OOOH
HO OH
methylation

Me
OOOMe
MeO OMe
eugenone
Biogenesis of phenols through shikimic acid. Biosynthesis
of shikimic acid
O
COO
PO
O
OH
OH
+
PO
HO
OH
OH
O
COO
OP
COOHO
OH
OHO
-H
2
O
NADPH
COO
OH
OH

HO
shikimic acid
Biosynthesis of aromatic amino acids through shikimic
acid
COO
OH
OH
PO
PO COO
H
+
COO
O
OH
PO
COOH
COO
OH
O COOH
[3,3]-Claisen
OP
OH
chorismic acid
OOC
COOH
O
prephenic acid
COOH
NH
2

COOH
NH
2
OH
tyrosine
phenylalanine
An overview of catabolic
pathways
Metabolism of fatty
acids
Metabolism of glucose (glycolysis)
Conversion of pyruvate
to acetyl coenzyme A
Anabolism of fatty acids
from CH
3
COSCoA
Anabolism of glucose
(gluconeogenesis)