682
INDEX
Diosgenin
as spiro compound 107
stereochemistry and shape 114
1,4-Dioxane, structure 404
1,3-Dioxolane, structure 404
Dipeptide, synthetic strategy 540
Diphenhydramine, structure 436
Diphosphates
in biochemical reactions 277
in intermediary metabolism 573
as leaving groups 196
1,3-Diphosphoglycerate
in glycolysis 581
as mixed anhydride 281
Diphosphoric acid, structure 277
Dipole
chloroform 36
furan 427
piperidine 406
pyridine 406
pyrrole 407, 427
pyrrolidine 407, 427
tetrahydrofuran 427
tetrahydrothiophene 427
thiophene 427
Dipole moment 36
Diradical, oxygen 333
Directing effects, of substituents in
electrophilic aromatic substitution,
Table 310
Disulfide bridge
definition 505
formation and cleavage 505
from glutathione 508
in insulin 506
oxidation 506
Di-tert-butyl peroxide 319
DNA (deoxyribonucleic acid) 228, 551–5
base pairing 432
chain, structure 552
circular 551
coding strand 555
copying via polymerase chain reaction
569
damage, from aflatoxins 202
double helix 552–3
hydrogen bonding 50
major and minor grooves 553
phosphodiesters in 276
pyrimidines 431
replication 553
synthesizers, automated 566
template strand 555, 556
DNA polymerase
in DNA replication 553
in polymerase chain reaction 569
as thiol nucleophile 399
DOPA (dihydroxyphenylalanine),
decarboxylation to dopamine
602
Dopamine
from decarboxylation of DOPA 602
structure 447
Double helix, DNA 552–3
Drugs, pKa values, Table 164
Drug absorption, and pK a 164
Dynorphin A, structure 515
Dynorphins 514
E and Z configurations, see configuration
E1 reactions 212–14
direction of elimination 212
mechanism 212
rate of reaction 212
rate-determining step 212
in tamoxifen synthesis 213
E1 or E2 reactions, according to substrate
214
E1cb elimination, in aldol reactions 362
E2 reactions 207–12
direction of elimination 209
energy diagram 209
Hofmann product 209
mechanism 207
with quaternary ammonium salts 210
rate of reaction 207
rate-determining step 207
Saytzeff product 209
stereochemistry 208
transition state 207
Eclipsed conformation, see conformation,
eclipsed
Edman degradation, N-terminal amino acid
determination 545
Edman reagent (phenyl isothiocyanate) 545
Elastase, specificity 521
Electrons 19
valence 19
Electron transport chain, in oxidative
phosphorylation 577
Electronegativity 23, 35, 49, 170
influence on acidity 125
influence on basicity 136
in S N 2 reactions 183
values, Pauling, Table 36
Electronic configuration
atoms 23
boron 23
carbon 23
energy diagrams 23
nitrogen 23
noble gases 23
oxygen 23
sp hybridized carbon 30
sp
2 hybridized carbon 28
sp
3 hybridized carbon 27
sp
3 hybridized nitrogen 33
sp
3 hybridized oxygen 33
Electrophiles
carbocations as 299
definition 171
in electrophilic aromatic substitution 304
examples 171
Electrophilic acylation, of aromatic rings 308
Electrophilic addition
to alkenes 283–92
anti-Markovnikov addition 286
carbocation rearrangements in 296
conjugated dienes, energy diagram 298
conjugated systems 296–9
energy diagram 284
halogens to alkenes 286–92
stereochemistry 287
hydrogen halides to alkenes 284–6
hydrogen halides to alkynes 292–4
intramolecular 300
Markovnikov’s rule 286
rate of reaction 283
rate-determining step 283
rearrangements in 217
regiochemistry 286
in terpenoid and steroid biosynthesis 300
Electrophilic alkylation
of aromatic rings 306–8
in steroid side-chain biosynthesis 294
Electrophilic aromatic substitution 304–17
anthracene 316
1,3-azoles 436
directing effects of substituents, Table 310
effect of substituents 309–14
indole 444
naphthalene 316
polycyclic compounds 315
pyridine 409
pyrrole 421
quinoline 440
Elimination reactions 175, 206–14
bimolecular see E2 reactions
E1cb mechanism 362
unimolecular see E1 reactions
Elimination or substitution reaction, according
to conditions 214
Enalapril, structure 532
Enamines
from aldehydes and ketones with amines
247
in aldolase mechanism 368, 526
alkylation 367
as analogues of enols 367
in biochemistry 366
formation, mechanism 248, 366
as nucleophiles 366–9
from TPP, in oxidative decarboxylation
606
in transamination 600
Enantiomers
definition 74
drawing 86
optical rotations 76
pharmacological properties 77
resolution 99
Enantiomeric excess, definition 77
Enantioselective synthesis 76
Enantiospecific synthesis 76
Enantiotopic
definition 94
faces 96
Cahn–Ingold–Prelog system 97
Endonucleases, restriction 564
Endorphins 514
β-endorphin, structure 515
Enediol, in glycolytic pathway 350
Energy barrier
chair conformations of cyclohexane 64
conformations of cyclobutane 61
conformations of cyclopentane 62
nitrogen inversion 74
rotation, butane 60
rotation, ethane 58
Energy diagram
conformations of butane 59
conformations of cyclohexane 66
conformations of ethane 59
E2 reaction 209
electrophilic addition reaction 284
INDEX
Diosgenin
as spiro compound 107
stereochemistry and shape 114
1,4-Dioxane, structure 404
1,3-Dioxolane, structure 404
Dipeptide, synthetic strategy 540
Diphenhydramine, structure 436
Diphosphates
in biochemical reactions 277
in intermediary metabolism 573
as leaving groups 196
1,3-Diphosphoglycerate
in glycolysis 581
as mixed anhydride 281
Diphosphoric acid, structure 277
Dipole
chloroform 36
furan 427
piperidine 406
pyridine 406
pyrrole 407, 427
pyrrolidine 407, 427
tetrahydrofuran 427
tetrahydrothiophene 427
thiophene 427
Dipole moment 36
Diradical, oxygen 333
Directing effects, of substituents in
electrophilic aromatic substitution,
Table 310
Disulfide bridge
definition 505
formation and cleavage 505
from glutathione 508
in insulin 506
oxidation 506
Di-tert-butyl peroxide 319
DNA (deoxyribonucleic acid) 228, 551–5
base pairing 432
chain, structure 552
circular 551
coding strand 555
copying via polymerase chain reaction
569
damage, from aflatoxins 202
double helix 552–3
hydrogen bonding 50
major and minor grooves 553
phosphodiesters in 276
pyrimidines 431
replication 553
synthesizers, automated 566
template strand 555, 556
DNA polymerase
in DNA replication 553
in polymerase chain reaction 569
as thiol nucleophile 399
DOPA (dihydroxyphenylalanine),
decarboxylation to dopamine
602
Dopamine
from decarboxylation of DOPA 602
structure 447
Double helix, DNA 552–3
Drugs, pKa values, Table 164
Drug absorption, and pK a 164
Dynorphin A, structure 515
Dynorphins 514
E and Z configurations, see configuration
E1 reactions 212–14
direction of elimination 212
mechanism 212
rate of reaction 212
rate-determining step 212
in tamoxifen synthesis 213
E1 or E2 reactions, according to substrate
214
E1cb elimination, in aldol reactions 362
E2 reactions 207–12
direction of elimination 209
energy diagram 209
Hofmann product 209
mechanism 207
with quaternary ammonium salts 210
rate of reaction 207
rate-determining step 207
Saytzeff product 209
stereochemistry 208
transition state 207
Eclipsed conformation, see conformation,
eclipsed
Edman degradation, N-terminal amino acid
determination 545
Edman reagent (phenyl isothiocyanate) 545
Elastase, specificity 521
Electrons 19
valence 19
Electron transport chain, in oxidative
phosphorylation 577
Electronegativity 23, 35, 49, 170
influence on acidity 125
influence on basicity 136
in S N 2 reactions 183
values, Pauling, Table 36
Electronic configuration
atoms 23
boron 23
carbon 23
energy diagrams 23
nitrogen 23
noble gases 23
oxygen 23
sp hybridized carbon 30
sp
2 hybridized carbon 28
sp
3 hybridized carbon 27
sp
3 hybridized nitrogen 33
sp
3 hybridized oxygen 33
Electrophiles
carbocations as 299
definition 171
in electrophilic aromatic substitution 304
examples 171
Electrophilic acylation, of aromatic rings 308
Electrophilic addition
to alkenes 283–92
anti-Markovnikov addition 286
carbocation rearrangements in 296
conjugated dienes, energy diagram 298
conjugated systems 296–9
energy diagram 284
halogens to alkenes 286–92
stereochemistry 287
hydrogen halides to alkenes 284–6
hydrogen halides to alkynes 292–4
intramolecular 300
Markovnikov’s rule 286
rate of reaction 283
rate-determining step 283
rearrangements in 217
regiochemistry 286
in terpenoid and steroid biosynthesis 300
Electrophilic alkylation
of aromatic rings 306–8
in steroid side-chain biosynthesis 294
Electrophilic aromatic substitution 304–17
anthracene 316
1,3-azoles 436
directing effects of substituents, Table 310
effect of substituents 309–14
indole 444
naphthalene 316
polycyclic compounds 315
pyridine 409
pyrrole 421
quinoline 440
Elimination reactions 175, 206–14
bimolecular see E2 reactions
E1cb mechanism 362
unimolecular see E1 reactions
Elimination or substitution reaction, according
to conditions 214
Enalapril, structure 532
Enamines
from aldehydes and ketones with amines
247
in aldolase mechanism 368, 526
alkylation 367
as analogues of enols 367
in biochemistry 366
formation, mechanism 248, 366
as nucleophiles 366–9
from TPP, in oxidative decarboxylation
606
in transamination 600
Enantiomers
definition 74
drawing 86
optical rotations 76
pharmacological properties 77
resolution 99
Enantiomeric excess, definition 77
Enantioselective synthesis 76
Enantiospecific synthesis 76
Enantiotopic
definition 94
faces 96
Cahn–Ingold–Prelog system 97
Endonucleases, restriction 564
Endorphins 514
β-endorphin, structure 515
Enediol, in glycolytic pathway 350
Energy barrier
chair conformations of cyclohexane 64
conformations of cyclobutane 61
conformations of cyclopentane 62
nitrogen inversion 74
rotation, butane 60
rotation, ethane 58
Energy diagram
conformations of butane 59
conformations of cyclohexane 66
conformations of ethane 59
E2 reaction 209
electrophilic addition reaction 284