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 [...]... OOC COO O phenylalanine COOH OH chorismic acid OH prephenic acid NH2 COOH tyrosine OH 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 CH3COSCoA Anabolism of glucose (gluconeogenesis) ...Biogenesis of phenols through shikimic acid Biosynthesis of shikimic acid O COO OH + PO PO O OP COO O HO OH OH OH COO HO COO -H2O O OH OH NADPH shikimic acid OH HO OH Biosynthesis of aromatic amino acids through shikimic acid COO COO + H PO COO O PO OH PO OP COOH OH OH NH2 [3,3]-Claisen O COOH COOH OOC COO O phenylalanine COOH OH chorismic acid OH prephenic acid NH2 COOH tyrosine OH An overview of catabolic . CHEMISTRY OF NATURAL PRODUCTS CHEMISTRY OF NATURAL PRODUCTS (professor Manolis Stratakis) Overview 1. Biosynthesis of terpenes 2. Biosynthesis of phenols 3 overview of catabolic pathways Metabolism of fatty acids Metabolism of glucose (glycolysis) Conversion of pyruvate to acetyl coenzyme A Anabolism of fatty