1. Chapter 28 (Secondary) Natural Products
Bioorganic Chemistry
Spring 2006
Chapter 28 (Secondary) Natural Products
Terpenes: from turpentine of pine trees;  1185
primary natural products: sugars, AAs, proteins, NAs
2 or more isoprene (C5H8): isoprenoids / terpenoids
monoterpenes (C10), sesquiterpenes (C15), diterpenes (C20), triterpenes (C30), tetraterpenes (C40): mostly head to tail
Monoterpenes from isopentenyl pyrophosphate
biosynthesis of geranyl pyrophosphate:  1188
isomerization to dimethylallyl-OPP:  1186 top
biosynthesis of isopentenyl pyrophosphate:  1186 bottom
other monoterpenes from neryl-OPP:  1189
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2. tail
head
‘terpenes’
‘terpenoids’
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5. pyruvate to acetyl CoA)
 (GAP to
pyruvate to acetyl CoA)
 882
 873
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7. Terpenes Sesquiterpenes from farnesyl pyrophosphate
Bioorganic Chemistry
Spring 2006
Terpenes
Sesquiterpenes from farnesyl pyrophosphate
formation of farnesyl-OPP:  1190 bottom
allylic carbocation after isomerization:  1191 top
tertiary carbocation (cascade cyclization):  1192 top
decalin rings: fused bicyclic system;  1192 bottom
conformation of cis- & trans-decalin: achiral;  1193
Diterpenes: geranylgeranyl-OPP;  1194
Triterpenes: 2 farnesyl-OPP (head-head);  1195
Tetraterpenes: 2 geranylgeranyl-OPP; 
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13. 2.7 kcal/mole lower than cis-decalin
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16. (red pigment in tomatoes)
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18. Lipids: Steroids Lipids: soluble in non-polar organic solvents
Bioorganic Chemistry
Spring 2006
Lipids: Steroids
Lipids: soluble in non-polar organic solvents
Cholesterol: key component of the membrane
lipophilic & rigid, cylindrical structure:  1196 & 1198
‘membrane plasticizer’: decreases membrane fluidity & inhibits crystallization of fatty acid side chains of the membrane lipids
biosynthesis from squalene via lanosterol:  1199
Other steroids: from cholesterol;  1200
Biomimetic synthesis: progesterone;  1201
semitotal synthesis: Syntex by R. Marker;  1202
synthesis of cortisone: anti-inflammatory;  1204
oral contraceptives: norethindrone, C. Djerassi;  1205
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21. phospholipids (phosphoglycerides)
(phosphotidylethanolamine: cephalin)
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22. cholesterol
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23. cholesterol
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27. Marketed in 1962 by Johnson & Johnson ‘Ortho-Novum’ pill
patented in 1951 by Syntex
Marketed in 1962 by Johnson & Johnson
‘Ortho-Novum’ pill
patented in 1953 by G. D. Searle & Co.
Marketed in 1960 by G. D. Searle & Co.
‘Enovid’ pill
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28. Lipids: Fats & Oils Triesters of glycerol & fatty acids:  1208
Bioorganic Chemistry
Spring 2006
Lipids: Fats & Oils
Triesters of glycerol & fatty acids:  1208
fatty acids (FAs): long & linear-chain carboxylic acids
even No of carbons: biosynthesis from acetate;  1209
common fatty acids & percentage in fats and oils
lower melting points of unsaturated FAs: bent structure
cis double bonds separated by one methylene (-CH2-) group
fats & oils-unsaturated FAs with ≥ two double bonds
glycerophopholipids: phosphotidyl choline;  1210
partial hydrogenation of vegetable oils: margarines;  1211
energy reserves: 6 times of energy of hydrated glycogen
waxes: esters from long-chain ROH & RCO2H
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29. (triacylglyceride)
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35. (phosphoacylglycerols)
(phosphotidylcholine: lecithin)
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36. (‘hardening of oils’)
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38. Lipids: Prostaglandins
Bioorganic Chemistry
Spring 2006
Lipids: Prostaglandins
Fatty acids with the prostanoic acid skeleton
various physiological functions:  1211
first found in semen (‘prostate gland’) by Euler but made in all cells except red blood cells (Bergström/Samuelsson/Vane)
biosynthesis: endroperoxide synthase;  1212
Alkaloids
Nitrogen-containing natural products: basic
readily isolated, mostly physiologically quite active & complex structure:  1206
structural similarity to amino acids:  1207
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39. prostaglandins: inflammatory response, production
of pain/fever, regulation of blood pressure, induction
of blood clotting, induction of labor, sleep-wake cycle
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40. thromboxanes (high pressure blood clotting) prostacyclins
(low pressure
inhibit aggregation)
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