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• Lipids include
–triglycerides, phospholipids,
prostaglandins, prostacyclins,
and fat-soluble vitamins
–cholesterol, steroid hormones,
and bile acids
Triglycerides
• Triglyceride: an ester of glycerol
with three fatty acids
O
O CH2 OCR CH2 OH RCOOH
1 . NaOH, H2 O
R'COCH O HOCH + R'COOH
2 . HCl, H2 O CH2 OH R''COOH
CH2 OCR''
A triglyceride 1,2,3-Prop anetriol Fatty acids
(Glycerol, glycerin)
4
Organic Lecture Series
Fatty acid
• Fatty acid: a carboxylic acid derived
from hydrolysis of animal fats,
vegetable oils, or membrane
phospholipids
– nearly all have an even number of
carbon atoms, most between 12 and 20,
in an unbranched chain
– the three most abundant are palmitic
(16:0), stearic acid (18:0), and oleic acid
(18:1)
5
O p almitate (16:0)
oleate (18:1)
O CH2 OC(CH2 ) 1 4 CH3
stearate (18:0)
CH3 ( CH2 ) 7 CH=CH(CH2 ) 7 COCH O
CH2 OC(CH2 ) 1 6 CH3
6
Organic Lecture Series
Fatty acid
–in most unsaturated fatty acids, the
cis isomer predominates; the trans
isomer is rare
–unsaturated fatty acids have lower
melting points than their saturated
counterparts; the greater the
degree of unsaturation, the lower
the melting point
Triglycerides
8
Organic Lecture Series
Triglycerides
–triglycerides rich in unsaturated
fatty acids are generally liquid at
room temperature and are
called oils
–triglycerides rich in saturated
fatty acids are generally
semisolids or solids at room
temperature and are called fats
9
Triglycerides
– example: a triglyceride derived from one
molecule each of palmitic acid, oleic acid, and
stearic acid, the three most abundant fatty
acids in the biological world
O p almitate (16:0)
oleate (18:1)
O CH2 OC(CH2 ) 1 4 CH3
stearate (18:0)
CH3 ( CH2 ) 7 CH=CH(CH2 ) 7 COCH O
CH2 OC(CH2 ) 1 6 CH3
10
Soaps and Detergents Organic Lecture Series
COO-Na+
11
13
14
Organic Lecture Series
Prostaglandins
• Prostaglandins: a family of compounds
that have the 20-carbon skeleton of
prostanoic acid
5 3 1
7
9
8 6 4 2 COOH
10
11 12 14 16 18 20
13 15 17 19
Prostanoic acid
15
11 12 14 15
Arachidonic acid 16
9 8 Organic Lecture Series
6 5
COOH
11 12 14 15
Arachidonic acid
17
Prostaglandins
• Research on the involvement of PGs in
reproductive physiology has produced
several clinically useful derivatives
– (15S)-15-methyl-PGF2α is used as a
therapeutic abortifacient
extra methyl group
HO at carb on -15
9
COOH
15
11
HO
HO CH3
(15S)-15-Methyl-PGF2α 18
Organic Lecture Series
Prostaglandins
the PGE1 analog, misoprostol, is used to prevent
the ulceration associated with the use of aspirin-
like NSAIDs* O
COOH
PGE1
16
15
HO
HO H
O
COOCH 3
Misoprostol
HO CH3
15 16
HO
Steroids
• Steroids: a group of plant and animal
lipids that have this tetracyclic ring
structure:
C D
A B
20
Organic Lecture Series
Steroids
– the fusion of rings is trans and each atom or
group at a ring junction is axial
– the pattern of atoms or groups along the ring
junctions is nearly always trans-anti-trans-
anti-trans
CH3
CH3 H
H
H
H 21
Cholesterol is the
Precursor for Families of
Steroids
22
Organic Lecture Series
Synthetic Anabolic Steroids
– a way to increase the testosterone concentration is to
use a “prohormone”, which the body converts to
testosterone; for example “andro”
OH
H3 CHO CH H3 C
3
H3 C
H3 C H
CH3 H
H H
H H
O O H
Meth androstenolon e Meth enolone
O
H3 C OC(CH2 ) 8 CH3 H3 C O
H CH3 H3 C H
H H H H
O O
N and rolon e decan oate 4-An dros tene-3,17-dione
23
(an dro)
H H
O
Progesterone 24
Organic Lecture Series
Cholesterol
H3 C
H3 C
H
H H
HO
25
OP2 O6 3 -
Isopentenyl pyrophosphate
Details
C10 terpenes ( C1 0 ) Geranyl pyrophosphate
Cholesterol 27
Isopentenyl
Dimethylallyl pyrophosphate
pyrophosphate
Geranyl
pyrophosphate
Details
28
Organic Lecture Series
Squalene
Oxide
4-ring closures
Form the
ABCD ring
system
29
HO
H
H
Loss of proton;
2 hydride and 2
methyl group
shifts gives H CH3
Lanosterol
CH3
HO
H
CH3
CH3
L a n o s te ro l
HO
30
Organic Lecture Series
H
CH3
CH3 SEVERAL
L a n o s te ro l STEPS
HO
H3 C
H3 C
H
H H
HO cholesterol
31
O HO CH3
O
-
CH3 -C- S- Co A O OH Details
Acetyl Coenzyme A (R)-Mevalonate
OP2 O6 3 -
Isopentenyl pyrophosphate
O
Equivalent to a
O O Claisen condensation
SCoA
SCoA
O
A c e to a c e ty l C o A
SCoA
A c e ty l C o A O H 3C OH O
O SCoA
β -h y d ro x y -β -m e th y lg lu ta ry l C o A
H M G -C o A 33
O H 3C OH O
β -h y d ro x y -β -m e th y lg lu ta ry l C o A
H M G -C o A
O SCoA
NADPH + 2H+
H M G -C o A re d u c ta s e
C oASH + 2N AD P+ T h is is in h ib ite d b y
th e "s ta tin " d ru g s
O H 3C OH OH
M e v a lo n a te
O
34
Organic Lecture Series
Atorvastatin
Lipitor
Simvastatin
Zocor
Lovastatin
Mevacor
Pravastatin
Pravacol 35