Mevalonate Pathway Terpenes & Steroids Reyes, Patrick A. BS Chemistry for Teachers Philippine Normal...
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![Page 1: Mevalonate Pathway Terpenes & Steroids Reyes, Patrick A. BS Chemistry for Teachers Philippine Normal University Taft Avenue, Manila.](https://reader035.fdocuments.in/reader035/viewer/2022062516/56649e2c5503460f94b1b26e/html5/thumbnails/1.jpg)
Mevalonate PathwayTerpenes & Steroids
Reyes, Patrick A.BS Chemistry for Teachers
Philippine Normal UniversityTaft Avenue, Manila
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• Also known as HMG –CoA (3-hydroxy-3-methylglutaryl CoenzymeA) or Mevalonate – dependent route
• Precursor of terpenes and steroids production
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MevalonatePathway
1st step
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Formation of HMG-CoA
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Acetyl CoA Acetoacetyl CoA HMG CoA
HMG CoA Synthase
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Formaton of Mevalonate
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HMG CoA Mevalonate
HMG CoA Reductase
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Formation of 5-phosphomavalonate
MevalonatePathway
5-phosphomevalonate
Mevalonate kinase
Mevalonate
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Formation of 5-pyrophospomevalonate
MevalonatePathway
5-phosphomevalonate 5-pyrophosphomevalonate
Phosphomevalonate Kinase
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Formation of IPP
MevalonatePathway
5-pyrophosphomevalonate
3-isopentyl pyrophosphate
Mevalonate-5-pyrophosphate decarboxylase
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Formation of DMAPP
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3-isopentyl pyrophosphate Dimethylallyl pyrophosphate
Isopentyl pyrophosphate isomerase
These five carbons are responsible for formation af all terpenes
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TERPENES
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Terpenes
• Terpenes are derived biosynthetically from units of isoprene
MevalonatePathway
C C
C C
C
isoprene isoprene unit
head
tail
natural rubber
D
C C
C
C C
.
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JOINING ISOPRENE UNITSHead-to-Tail
Tail-to-Tail
The terms head-to-tail andtail-to-tail are often used todescribe how the isopreneunits are joined.
an extrabond
larger terpenoidunits dimerizetail-to-tail
individualisoprene units join head-to-tail
….. explained later
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CLASSIFICATION OF TERPENES
TYPE OF NUMBER OF ISOPRENE TERPENE CARBON ATOMS UNITS
hemiterpene
terpene
sesquiterpene
diterpene
triterpene
tetraterpene
C5
C10
C15
C20
C30
C40
one
two
three
four
six
eight
hemi = half di = twosesqui = one and a half tri = three
tetra = four
NOTE:
sesterterpene C25 five
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SOME TERPENES (C10)CH2OH
OH
a-pinenecamphor
geraniol mentholrose and other flowers peppermint
camphor tree turpentine
O
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SESQUITERPENES
CH3
CH3
CH CH3
CH3guaiazulenegeranium oil
CH3
CH3
CH3
caryophyllene
oil of cloves
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MevalonatePathway
HOW TERPENES ARE FORMED?
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CH2H
CH2
CH3
OPP
CH3H
CH2
CH3
OPP
IPP DMAPP
CH3
CH2
H
OPPCH2OPP
CH2 OPP
H
OPP
C5 C10
CH2 OPP
CH2 OPP
C15C20
C5isopentenyl-PP3,3-dimethylallyl-PP
C10geranyl-PP
C15
farnesyl-PP
C20
geranyl-geranyl-PP
CONCATENATION OF C5 (ISOPRENE) UNITS
:B
again
TAIL
HEAD
EACH NEW UNIT IS JOINED HEAD-TO-TAIL
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DIMERIZATION OF C15 AND C20 UNITS
CH2
CH3
R
OPPC
CH3
O
R
PO O
O
CH2
CH3
R
PO O
O
CH
CH3
O
R
H
CH3
R
PO O
O
CH3
O
R
CH2
CH
CH3
RH
CH3
R
H:-
NADH NAD+
Enz-B:
P OO
O
O
CH2
CH3 R
rearrange
dimerize
TAIL
TAIL
JOINED SYMMETRICALLY TAIL-TO-TAILUNITS ARE JOINED TAIL-TO-TAIL
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