INDEX
683
electrophilic addition to conjugated dienes
298
S N 1 reaction 192
S N 2 reaction 184
Enkephalins 514
Leu-enkephalin, structure 515
Met-enkephalin, structure 515
Enols 347
and enolization, in glycolytic pathway
350
Enolase, in glycolysis 583
Enolate anions 130, 156
acylation, see Claisen reaction
from aldehydes and ketones 349
in aldol reaction 360–5
alkylation 357–60
amount at equilibrium 159
as bases 352
in biochemistry 523–9
from carboxylic acid derivatives 372–9
alkylation 378
in aldol reaction 379
and conjugation 354
definition 349
from diethyl malonate 390
halogenation involving 356
in isotopic labelling 158
as nucleophiles, alkylation 357
resonance stabilization 349
using strong bases 358
Enolization
acid-catalysed mechanism 348
base-catalysed mechanism 349, 523
in biochemistry 523–9
definition 347
enzyme-catalysed mechanism 523
interconversion of monoterpenes 353
of glucose 467
keto–enol 341
triose phosphate isomerase mechanism
524
Enolpyruvic acid, in glycolysis 584
Enoyl-CoA hydratase, in fatty acid
β-oxidation 591
Envelope conformation, cyclopentane 62
Enzymes
acid–base catalysis 516
binding via imine formation 516
binding via thioester formation 516
definition 515
multifunctional, definition 530
pH optimum 517
in resolution of enantiomers 100
stereospecificity 96
Enzyme action
binding sites 515
mechanisms 515–30
Enzyme complex, definition 530
Enzyme inhibitors 530–2
allosteric 532
competitive 531
irreversible 531
non-competitive 531
reversible 531
Ephedrine
enantiomers 85
in resolution of enantiomers 99
Epigallocatechin gallate, as antioxidant 338
Epimer
definition 86
drawing 86
in glucose stereoisomers 104
Epimerase, in unsaturated fatty acid
metabolism 593
Epimerization, of glucose 467
Epinephrine, see adrenaline
Epoxides
from aflatoxins 203
from halohydrins 289
hydrolysis 199
nucleophilic ring opening 290
in nucleophilic substitution reactions 199
using peracids 290
mechanism 290
reaction with Grignard reagents 204
reaction with lithium aluminium hydride
206
Epoxycyclohexane, stereochemistry 111
Equatorial groups, cyclohexane 64
Equilibria, acid–base 121
Ergosterol
in fungi 294
stereochemistry and shape 113
Erythromycin, structure 256, 494
Erythrose, structure and stereochemistry 465
Eserine, structure 448
Esters
acidity 372
basicity 139
conjugated 396
cyclic see lactones
formation, from acid and alcohol,
acid-catalysed 252
formation, from acyl halides and
anhydrides 253
hydrolysis
acid-catalysed 257, 516
base-catalysed 258, 517
general acid-catalysed 518
general base-catalysed 518
from nucleophilic substitution reactions 198
synthesis of amides 263
as temporary activating group 391
by transesterification 254
Esterases 202, 211
Esterification, sugars, anomeric centre 473
Ester–ketone condensations, predicting the
product 384
Estradiol
stereochemistry and shape 114
structure 241
Estrone, synthesis of ethinylestradiol 241
Ethane
acidity 128
bonding molecular orbitals 28
conformational isomers 57
Ethanol, in glycolysis 584
Ethchlorvynol, nomenclature 11
Ethers
basicity 138
from nucleophilic substitution reactions
198
Ethinylestradiol, synthesis from estrone 241
Ethyl acetoacetate
acidity 380
from Claisen reaction 379
Ethylene
acidity 128
bonding molecular orbitals 29
Ethylene imine, structure 404
Ethylene oxide
shape 72
structure 404
Ethylene sulfide, structure 404
Ethyne, see acetylene
Etoposide
acetal linkages 233
isomerization 111
Excited state 25
FAD (flavin adenine dinucleotide)
as nucleotide 560
structure 456
FAD and FMN
in biological oxidations 576
in oxidation–reduction sequences 456
FADH 2 and FMNH 2 , in biological reductions
576
Farnesyl diphosphate
allylic cation 197
in terpenoid and steroid biosynthesis 301
Fats and oils
autoxidation and rancidity 334
base hydrolysis 258
Fatty acids
biosynthesis 594–8
conversion to CoA esters 590
from hydrolysis of fats 590
saturated, metabolism 590
unsaturated, metabolism 592
β-oxidation 387, 589–92
Fatty acid synthase 595–8
dimeric 597
mechanism 597
Fatty acyl-AMP 590
as mixed anhydride 282
Fatty acyl-CoA, from fatty acids 591
Fischer indole synthesis 461
Fischer projections 100–6
D and L amino acids 106
carbohydrates 464
assigning chirality 102
definition 100
glucose and stereosiomers 104
manipulation 101
Flagpole interaction, cyclohexane boat
conformation 66
Flavanone, class of flavonoid 396
Flavin adenine dinucleotide, see FAD
Flavin mononucleotide, see FMN
Flavonoids
as antioxidants 337, 396
conjugate addition 396
as pyrones 418
Flavoproteins, in biological oxidations
576
Fludrocortisone acetate, structure 292
Fluoride, as leaving group in nucleophilic
aromatic substitution 544
FMN (flavin mononucleotide)
as nucleotide 560
structure 456
683
electrophilic addition to conjugated dienes
298
S N 1 reaction 192
S N 2 reaction 184
Enkephalins 514
Leu-enkephalin, structure 515
Met-enkephalin, structure 515
Enols 347
and enolization, in glycolytic pathway
350
Enolase, in glycolysis 583
Enolate anions 130, 156
acylation, see Claisen reaction
from aldehydes and ketones 349
in aldol reaction 360–5
alkylation 357–60
amount at equilibrium 159
as bases 352
in biochemistry 523–9
from carboxylic acid derivatives 372–9
alkylation 378
in aldol reaction 379
and conjugation 354
definition 349
from diethyl malonate 390
halogenation involving 356
in isotopic labelling 158
as nucleophiles, alkylation 357
resonance stabilization 349
using strong bases 358
Enolization
acid-catalysed mechanism 348
base-catalysed mechanism 349, 523
in biochemistry 523–9
definition 347
enzyme-catalysed mechanism 523
interconversion of monoterpenes 353
of glucose 467
keto–enol 341
triose phosphate isomerase mechanism
524
Enolpyruvic acid, in glycolysis 584
Enoyl-CoA hydratase, in fatty acid
β-oxidation 591
Envelope conformation, cyclopentane 62
Enzymes
acid–base catalysis 516
binding via imine formation 516
binding via thioester formation 516
definition 515
multifunctional, definition 530
pH optimum 517
in resolution of enantiomers 100
stereospecificity 96
Enzyme action
binding sites 515
mechanisms 515–30
Enzyme complex, definition 530
Enzyme inhibitors 530–2
allosteric 532
competitive 531
irreversible 531
non-competitive 531
reversible 531
Ephedrine
enantiomers 85
in resolution of enantiomers 99
Epigallocatechin gallate, as antioxidant 338
Epimer
definition 86
drawing 86
in glucose stereoisomers 104
Epimerase, in unsaturated fatty acid
metabolism 593
Epimerization, of glucose 467
Epinephrine, see adrenaline
Epoxides
from aflatoxins 203
from halohydrins 289
hydrolysis 199
nucleophilic ring opening 290
in nucleophilic substitution reactions 199
using peracids 290
mechanism 290
reaction with Grignard reagents 204
reaction with lithium aluminium hydride
206
Epoxycyclohexane, stereochemistry 111
Equatorial groups, cyclohexane 64
Equilibria, acid–base 121
Ergosterol
in fungi 294
stereochemistry and shape 113
Erythromycin, structure 256, 494
Erythrose, structure and stereochemistry 465
Eserine, structure 448
Esters
acidity 372
basicity 139
conjugated 396
cyclic see lactones
formation, from acid and alcohol,
acid-catalysed 252
formation, from acyl halides and
anhydrides 253
hydrolysis
acid-catalysed 257, 516
base-catalysed 258, 517
general acid-catalysed 518
general base-catalysed 518
from nucleophilic substitution reactions 198
synthesis of amides 263
as temporary activating group 391
by transesterification 254
Esterases 202, 211
Esterification, sugars, anomeric centre 473
Ester–ketone condensations, predicting the
product 384
Estradiol
stereochemistry and shape 114
structure 241
Estrone, synthesis of ethinylestradiol 241
Ethane
acidity 128
bonding molecular orbitals 28
conformational isomers 57
Ethanol, in glycolysis 584
Ethchlorvynol, nomenclature 11
Ethers
basicity 138
from nucleophilic substitution reactions
198
Ethinylestradiol, synthesis from estrone 241
Ethyl acetoacetate
acidity 380
from Claisen reaction 379
Ethylene
acidity 128
bonding molecular orbitals 29
Ethylene imine, structure 404
Ethylene oxide
shape 72
structure 404
Ethylene sulfide, structure 404
Ethyne, see acetylene
Etoposide
acetal linkages 233
isomerization 111
Excited state 25
FAD (flavin adenine dinucleotide)
as nucleotide 560
structure 456
FAD and FMN
in biological oxidations 576
in oxidation–reduction sequences 456
FADH 2 and FMNH 2 , in biological reductions
576
Farnesyl diphosphate
allylic cation 197
in terpenoid and steroid biosynthesis 301
Fats and oils
autoxidation and rancidity 334
base hydrolysis 258
Fatty acids
biosynthesis 594–8
conversion to CoA esters 590
from hydrolysis of fats 590
saturated, metabolism 590
unsaturated, metabolism 592
β-oxidation 387, 589–92
Fatty acid synthase 595–8
dimeric 597
mechanism 597
Fatty acyl-AMP 590
as mixed anhydride 282
Fatty acyl-CoA, from fatty acids 591
Fischer indole synthesis 461
Fischer projections 100–6
D and L amino acids 106
carbohydrates 464
assigning chirality 102
definition 100
glucose and stereosiomers 104
manipulation 101
Flagpole interaction, cyclohexane boat
conformation 66
Flavanone, class of flavonoid 396
Flavin adenine dinucleotide, see FAD
Flavin mononucleotide, see FMN
Flavonoids
as antioxidants 337, 396
conjugate addition 396
as pyrones 418
Flavoproteins, in biological oxidations
576
Fludrocortisone acetate, structure 292
Fluoride, as leaving group in nucleophilic
aromatic substitution 544
FMN (flavin mononucleotide)
as nucleotide 560
structure 456