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TERPENES
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C C
C C
C
isoprene isoprene
unit
head
tail
TERPENES
The Czech chemist Leopold Ruzicka ( born 1887 sho!ed that
man" compounds #ound in nature !ere #ormed #rom multipleso# $%e carbons arran&ed in the same pattern as an isoprenemolecule (obtained b" p"rol"sis o# natural rubber'
e called these compounds )terpenes*'
natural
rubber
C C
C
C C
.
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+,-N-N. -S,PRENE /N-TS
ead0to0Tail
Tail0to0Tail
The terms head0to0tail andtail0to0tail are o#ten used todescribe ho! the isopreneunits are oined'
an e2trabond
lar&er terpenoidunits dimerizetail0to0tail
indi%idualisoprene unitsoin head0to0tail
3'' e2plained later 3
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limonene dia&ram sho!in& ho! t!oisoprene units combine to#orm the limonene skeleton
from lemon and
orange peels
TERPENES C4N 5E S,6N T, 5E,RE9 R, -S,PRENE /N-TS
head totail
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Beberapa contoh senyawa terpena
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E:4L,N-C 4C-9 P4T64;
TERPENES
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4CET;L Co4 /N-TS 4RE L-N
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CH2
C
S
O
CoAC
O
OH
malon"l Co4
Enz05=
C
O
CH3
S CoA
acet"l Co4
0 C,@
CH2
C S
O
CoA
O CH3
C
O
O''
TE ENA;ES T4T 4SSE5LE 4CET;L0Co4 /N-TS /SE 4 9EC4R5,B;L4T-,N , 4L,N;L0Co4
4 )REE* EN,L4TE -,N -S NE:ER ,RE9
CH2
CS
O
CoAC
O
OH
Enz05=''
CH2
CCH
2
O
C
O CH3
S CoA
O
CH3
C
O
CH2
C
O
CH2
C
O
CH2
C
O
CH2
C
O
SCoA
a pol"ketide chain
2@
2
2D 2
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)ST4RTER*
)C4-N EBTEN9ER*
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CH2
CS
O
CoAC
O
OH
C
O
CH3
S CoA
0 C,@
CH2
C
S CoA
C
CH3
O O
''
CH2
CCH
2
O
C
O
CCH
3
O
SCoA
P,L;
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C
CH2
CH2
CH3
OH C
C
O
O
SCoA
SCoA
acet"lCo4 C
CH2
CH2
CH3
OH C
C
O
O
SCoA
SCoA
H
C
CH2
CH2
CH3
OH C
C
O
O
SCoA
H
C
CH2
CH2
CH3
OH C
CH2
O
SCoA
OH
C
CH2
CH2
CH3
OH C
CH2
O
OH
OH
me%alonic acid
E:4L,N-C 4C-9 P4T64;,R4T-,N , E:4L,N-C 4C-9 R, 4CET;L /N-TS
N49P
N49P@,
''= =0
1!
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C
CH2
CH2
CH3
OH C
CH2
O
OH
OH
me%alonic acid
C
CH2
CH2
CH3
O C
CH2
O
O
O
P H
P P
=50Enz
@ 4TP
49P
4P
CH2H
CH2
CH3
OPP
CH3H
CH2
CH3
OPP
F0dimeth"lall"lp"rophosphate
isopenten"lp"rophosphate
Enz05= G
E:4L,N-C 4C-9 P4T64;The isopenten"l and F0dimeth"lall"l p"rophosphate intermediates
These $%e0carbonintermediates areresponsible #or the#ormation o# all theterpenes'
94PP -PP
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,6 TE TERPENES 4RE ,RE9
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CH2
H
CH2
CH3
OPP
CH3
H
CH2
CH3
OPP
-PP 94PP
CH3
CH2
H
OPPCH2
OPP
CH2
OPP
H
OPP
CD C1H
CH2
OPP
CH2
OPP
C1DC@H
CDisopenten"l0PP
F0dimeth"lall"l0PP
C1H&eran"l0PP
C1D#arnes"l0PP
C@H&eran"l0&eran"l0PP
C,NC4TEN4T-,N , CD (-S,PRENE /N-TS
=5
a&ain
T4-L
E49
E4C NE6 /N-T -S +,-NE9 E490T,0T4-L13
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CL4SS--C4T-,N , TERPENES
T;PE , N/5ER , -S,PRENETERPENE C4R5,N 4T,S /N-TS
hemiterpene
terpenesesIuiterpene
diterpene
triterpenetetraterpene
CD
C1H C1D C@H
CH
CH
one
t!o three
#our
si2 ei&ht
hemi J hal# di J t!osesIui J one and a hal# tri J three
tetra J #our
N,TE=
sesterterpene C@D$%e
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S,E TERPENES (C1H
C"2#"
#"
0pinenecamphor
&eraniol mentholrose and other flowers peppermint
camphor tree turpentine
#
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(+0car%one J cara!a" seed
(-0car%one J spearmint(+0limonene J oran&es
(-0 limonene J lemons
ost c"clic monoterpenes ha%e a distincti%e odor 0 basis o# per#ume K a%or industries
Stereoisomersha%e di>erent characteristic smells 0 demonstrates that smell receptors are 9 proteinsFi'e' chiral en%ironments that can distin&uish enantiomers
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SESM/-TERPENES
CH3
CH3
CH CH3
CH3&uaiazulene
&eranium oil
CH3
CH3
CH3
car"oph"llene
oil o# clo%es17
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cedrenecedar !ood oil
CH3
CH3
CH3 CH3
CH3
CH3
H3C
lon&i#olenepine species
3'' more sesIuiterpenes
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Biosynthesis of $es%uiterpenes &C15'
rearran&ed to #ormsesquiterpenes(C15
Geranylp"rophosphate(C10
Farnesylp"rophosphate(C15
Pren"l trans#erase G
94P -PP
0 i# "ou introduce a labeled carbon in the
precursorF "ou can see !here it ends up in the $nal natural product
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Biosynthesis of $es%uiterpenes &C15'
rearran&ed to #ormsesquiterpenes(C15
Geranylp"rophosphate(C10
Farnesylp"rophosphate(C15
Pren"l trans#erase G
94P -PP
0 i# "ou introduce a labeled carbon in the
precursorF "ou can see !here it ends up in the $nal natural product
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(abeling studies in Biosynthesis 1
/sin& isotopicallyenrichedprecursorsF it is possible to trace the incorporation o# buildin& blocks into comple2 metabolites
0 #ollo! the label and see !hich atoms in the natural product end up labeled
,ri&inall" done !ith radioactivelabels(14
CF3
0 #eed cells a precursor !ith one 14C
0 use chemical de"radationto break natural product apartFsee !hich pieces contain the radioacti%it"
0 dra!back= slopp"F usuall" not possible to completel"determine bios"nthetic route
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(abeling studies in Biosynthesis 2
No! done b" NR usin& non-radioactiveisotope
13
C 0 common carbon isotope 1@C is in%isible to NR
0 rare 13Chas nuclear spin IJ n@F so is detectable b" NR
0 #eed cells a precursor !ith one position 13ClabeledO
then see !hich positions sho! e2a&&erated peaks in the carbon NR spectrum
since onl" 1 o# carbons are naturall" 13CF the positions that incorporate the label !ill &i%e much hi&her peaks
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1C NR spectrum o# compound #F a#ter #eedin& sea slu& !ithQ@01C me%alonate 0 increased size o# peaks sho!s label incorporation
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0 allo!ed researchers to in#er bios"nthetic path!a" #or these related C0@ and C0@1 terpenes
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C"3
C"3
C"3
C"3
#"
C"3
C"3C"3
ambreinamber&is
TR-TERPENES
T4-L0T,0T4-L
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4ll steroids are triterpenesbut their skeletons ha%e beenrearran&ed so that the" cannot be anal"zed into isopreneunits'
C"3
C"3
C"3
C"3
C"3 C"3
"#
rearran&ementsin this area
STER,-9S 4RE TR-TERPENES (CH
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0carotene
carrots
TETR4TERPENE
tail0to0tailhead0to0tail
head0to0tail
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C,NC4TEN4T-,N , CD (-S,PRENE /N-TS
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CH2
H
CH2
CH3
OPP
CH3
H
CH2
CH3
OPP
-PP 94PP
CH3
CH2
H
OPPCH2
OPP
CH2
OPP
H
OPP
CD C1H
CH2
OPP
CH2
OPP
C1DC@H
CDisopenten"l0PP
F0dimeth"lall"l0PP
C1H&eran"l0PP
C1D#arnes"l0PP
C@H&eran"l0&eran"l0PP
C,NC4TEN4T-,N , CD (-S,PRENE /N-TS
=5
a&ain
T4-L
E49
E4C NE6 /N-T -S +,-NE9 E490T,0T4-L 28
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CH 4N9 CH /N-TS 4RE ,RE9 9-ERENTL;
E-TERPENES CD 1 -PP or 94PP
,N,TERPENES C1H@ &eran"l0PP
SESM/-TERPENES C1D #arnes"l0PP
9-TERPENES C@H &eran"l0&eran"l0PP
C@DD uncommon
TR-TERPENES CH @ 2 (#arnes"l0PP
CD7 uncommon
TETR4TERPENES CH8 @ 2 (&eran"l0&eran"l0PP
Class o# Carbons /nits ,ri&in
-sopreneNumber
2@
2@
SESTERTERPENE
2
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9-ER-A4T-,N , C1D 4N9 C@H /N-TS
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
=0
N49 N49G
Enz05=
P OO
O
O
CH2
CH3 R
rearran&e
dimerize
T4-L
T4-L
+,-NE9S;ETR-C4LL;
T4-L0T,0T4-L/N-TS 4RE +,-NE9 T4-L0T,0T4-L 3!
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C,,N TERPEN,-9 S
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TERPEN,-9S
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H
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OPP
H
O
OH
H
OOH
HH
&eran"l0PP (.PP
OPP
linal"l0PP (LPP
&eraniol&eranium oil
&eranial&eranium oil
citronellol
citronellal
rose oil
citronella oil
OPP
ner"l0PP (NPP
OH
0m"rcenehops
linaloolcoriander oil
H
O
OH
nerallemon oil
nerolrose oil
OH
0terprneol 33
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OPP
G
G
LPP
,PP0
or
G
GG
0pinene
0pinene
G
OHO
#enchol#enchone
1F@0alk"lshi#t
0 G
0 G
@,
N49PG
ionize
OH
O
G
0 G
camphene
borneol
camphor
1F@0alk"lshi#t
@,
N49PG
meth"l
0terpin"l cation
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T4B,L
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T4B,L
OPP
G
(G
GH
H
G
G
ta2adiene
OOOO
OH
OH
OH O OH
CH3
O
H
OOOO
OH
O
O O OH
CH3
O
H
O
OH
NHO
CH3
O
paclita2el(ta2ol
man" steps=o2idationsF
esteri$cation
Phe
Phe
Phe
acet"lCo4
acet"lCo4
Paci$c ;e! (bark
1HH0"r0old trees J 1 &
/sed clinicall" in treatmento# breastF o%arianF lun&FheadF neck cancers'
..PP
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