680
INDEX
Cephalosporins
as amides/lactams 265
mode of action 539
as modified tripeptides 537
stereochemistry and shape 116
Chain reaction, radical see radical chain
reaction
Chair conformation
cyclohexane 62
how to draw 63
interconversion 64
Chalcone, class of flavonoid 396
Charge-relay network
in acetylcholinesterase mechanism 521
in chymotrypsin mechanism 523
Chichibabin reaction
imidazole 437
isoquinoline 443
pyridine 411
quinoline 441
Chiral centre, definition 73
Chirality
allenes 92
biphenyls 92
without chiral centres 92–4
definition 73
quaternary nitrogen compounds 74
spiro compounds 93
Chitin, structure 495
Chitosan 495
Chloral hydrate 234
Chlorination, radical, alkanes 324
Chloronium ion, in addition of halogens to
alkenes 287
m-Chloroperbenzoic acid (MCPBA), in
formation of N-oxides 410
Chlorophyll, structure 424
Chloropyridines 411, 417
Cholestane, stereochemistry and shape 112
Cholestenone, from cholesterol 355
Cholesterol
conversion into cholestenone 355
lanosterol as precursor 219
in mammals 294
mevalonic acid as precursor 381
stereochemistry and shape 113
Cholic acid, stereochemistry and shape 114
Chrysanthemic acid, structure 61
Chymotrypsin
enzyme mechanism 521–3
in peptide sequence determination 546
specificity 521
Ciclosporin
D amino acids in 376
structure 536
Cimetidine, structure 436
Cineole, biosynthesis 303
Cinerolone, structure 61
Ciprofloxacin, structure 442
cis and trans, see configuration
peptide bond 509
Citrate synthase
as aldol reaction 363
enzymic mechanism 528
in Krebs cycle 586
Citric acid
via aldol reaction, Krebs cycle 363,
585
cycle, see Krebs cycle
prochirality 95, 586
Citryl-CoA, in Krebs cycle 585
Cladinose, in erythromycin 256, 494
Claisen and aldol reactions, in phenol
biosynthesis 385
Claisen reaction 379–83
intramolecular (Dieckmann reaction) 382
in phenol biosynthesis 385
ring size 382
involving acetyl-CoA 595
involving malonyl-CoA 595
ionization of product 380
mechanism 380
mixed/crossed 382
in nature 381
involving malonyl-CoA 392
reverse 386, 391
Clomifene, configuration 84
Cocaine, stereochemistry and shape 118
Codeine
in morphine biosynthesis 343
in opium 343
from selective alkylation of morphine 186
Codon
combinations, Table 555
definition 555
Coenzyme
in biological oxidations 575
definition 515
Coenzyme A
as nucleotide 229, 560
structure 585
as thiol 262, 373
Coenzyme Q (ubiquinone), in electron
transport chain 577
Computer graphics, molecular models 52
Concerted reaction
E2 reactions 207
S N 2 reactions 183
Configuration
amino acids 81
6-aminopenicillanic acid 82
chiral centres, Cahn–Ingold–Prelog system
80–2
cis and trans 68, 84
clomifene 84
and conformation, avoiding confusion 88
cyclic compounds 82
D and L 103–6
definition 74
double bonds, Cahn–Ingold–Prelog system
84
E, Z convention for double bonds 84
electronic 23
pro-R, pro-S convention for prochiral
centres 95
R, S convention for chiral centres 80–2
Re, Si convention for enantiotopic faces 97
tamoxifen 84
triprolidine 85
Configurational isomers 68, 73–106
decalins 109
definition 57
hydrindanes 110
several chiral centres 85–9
Conformation
anti 59
boat, cyclohexane 65
chair, cyclohexane 62
and configuration, avoiding confusion 88
eclipsed 58
envelope, cyclopentane 62
gauche 59
half-chair, cyclohexene 67
tetrahydronaphthalene 67
staggered 58
twist-boat
cyclohexane 66
di-tert-butylcyclohexanes 72
Conformational isomers
acyclic compounds 57–60
butane 58
energy diagram 59
tert-butylcyclohexane 68
cyclic compounds 60–73
cyclic hemiacetals of sugars 471
cyclic sugars, descriptors 472
cyclobutane 60
cyclohexane 62
energy diagram 66
cyclohexane rings, how to draw 70
cyclopentane 62
cyclopropane 60
cis-decalin 107
definition 57
1,4-dimethylcyclohexane 68
dimethylcyclohexanes 69
ethane 57
energy diagram 59
glycosides 475
heterocycles 72
cis-hydrindane 110
myo-inositol 70
lindane 73
menthol 70
methylcyclohexane 67
neoisomenthol 70
quinic acid 70
Conformers see conformational isomers
Conjugate acid
aldehydes and ketones 221
definition 121
Conjugate addition
to conjugated carbonyl derivatives 394
definition 297
of enolate anions, see Michael reaction
flavonoids 396
radical addition of HBr to conjugated
dienes 330
multiple 400
Conjugate base, definition 121
Conjugated
bonds 37
carbonyl derivatives
nucleophilic addition 393–401
resonance structures 393
dienes, radical addition of HBr 330
esters 396
nitriles 396
systems, electrophilic addition reactions
296–9
Conjugation 37–41
delocalization of electrons 38
via enolate anion 354
Constitutional isomers, definition 56
INDEX
Cephalosporins
as amides/lactams 265
mode of action 539
as modified tripeptides 537
stereochemistry and shape 116
Chain reaction, radical see radical chain
reaction
Chair conformation
cyclohexane 62
how to draw 63
interconversion 64
Chalcone, class of flavonoid 396
Charge-relay network
in acetylcholinesterase mechanism 521
in chymotrypsin mechanism 523
Chichibabin reaction
imidazole 437
isoquinoline 443
pyridine 411
quinoline 441
Chiral centre, definition 73
Chirality
allenes 92
biphenyls 92
without chiral centres 92–4
definition 73
quaternary nitrogen compounds 74
spiro compounds 93
Chitin, structure 495
Chitosan 495
Chloral hydrate 234
Chlorination, radical, alkanes 324
Chloronium ion, in addition of halogens to
alkenes 287
m-Chloroperbenzoic acid (MCPBA), in
formation of N-oxides 410
Chlorophyll, structure 424
Chloropyridines 411, 417
Cholestane, stereochemistry and shape 112
Cholestenone, from cholesterol 355
Cholesterol
conversion into cholestenone 355
lanosterol as precursor 219
in mammals 294
mevalonic acid as precursor 381
stereochemistry and shape 113
Cholic acid, stereochemistry and shape 114
Chrysanthemic acid, structure 61
Chymotrypsin
enzyme mechanism 521–3
in peptide sequence determination 546
specificity 521
Ciclosporin
D amino acids in 376
structure 536
Cimetidine, structure 436
Cineole, biosynthesis 303
Cinerolone, structure 61
Ciprofloxacin, structure 442
cis and trans, see configuration
peptide bond 509
Citrate synthase
as aldol reaction 363
enzymic mechanism 528
in Krebs cycle 586
Citric acid
via aldol reaction, Krebs cycle 363,
585
cycle, see Krebs cycle
prochirality 95, 586
Citryl-CoA, in Krebs cycle 585
Cladinose, in erythromycin 256, 494
Claisen and aldol reactions, in phenol
biosynthesis 385
Claisen reaction 379–83
intramolecular (Dieckmann reaction) 382
in phenol biosynthesis 385
ring size 382
involving acetyl-CoA 595
involving malonyl-CoA 595
ionization of product 380
mechanism 380
mixed/crossed 382
in nature 381
involving malonyl-CoA 392
reverse 386, 391
Clomifene, configuration 84
Cocaine, stereochemistry and shape 118
Codeine
in morphine biosynthesis 343
in opium 343
from selective alkylation of morphine 186
Codon
combinations, Table 555
definition 555
Coenzyme
in biological oxidations 575
definition 515
Coenzyme A
as nucleotide 229, 560
structure 585
as thiol 262, 373
Coenzyme Q (ubiquinone), in electron
transport chain 577
Computer graphics, molecular models 52
Concerted reaction
E2 reactions 207
S N 2 reactions 183
Configuration
amino acids 81
6-aminopenicillanic acid 82
chiral centres, Cahn–Ingold–Prelog system
80–2
cis and trans 68, 84
clomifene 84
and conformation, avoiding confusion 88
cyclic compounds 82
D and L 103–6
definition 74
double bonds, Cahn–Ingold–Prelog system
84
E, Z convention for double bonds 84
electronic 23
pro-R, pro-S convention for prochiral
centres 95
R, S convention for chiral centres 80–2
Re, Si convention for enantiotopic faces 97
tamoxifen 84
triprolidine 85
Configurational isomers 68, 73–106
decalins 109
definition 57
hydrindanes 110
several chiral centres 85–9
Conformation
anti 59
boat, cyclohexane 65
chair, cyclohexane 62
and configuration, avoiding confusion 88
eclipsed 58
envelope, cyclopentane 62
gauche 59
half-chair, cyclohexene 67
tetrahydronaphthalene 67
staggered 58
twist-boat
cyclohexane 66
di-tert-butylcyclohexanes 72
Conformational isomers
acyclic compounds 57–60
butane 58
energy diagram 59
tert-butylcyclohexane 68
cyclic compounds 60–73
cyclic hemiacetals of sugars 471
cyclic sugars, descriptors 472
cyclobutane 60
cyclohexane 62
energy diagram 66
cyclohexane rings, how to draw 70
cyclopentane 62
cyclopropane 60
cis-decalin 107
definition 57
1,4-dimethylcyclohexane 68
dimethylcyclohexanes 69
ethane 57
energy diagram 59
glycosides 475
heterocycles 72
cis-hydrindane 110
myo-inositol 70
lindane 73
menthol 70
methylcyclohexane 67
neoisomenthol 70
quinic acid 70
Conformers see conformational isomers
Conjugate acid
aldehydes and ketones 221
definition 121
Conjugate addition
to conjugated carbonyl derivatives 394
definition 297
of enolate anions, see Michael reaction
flavonoids 396
radical addition of HBr to conjugated
dienes 330
multiple 400
Conjugate base, definition 121
Conjugated
bonds 37
carbonyl derivatives
nucleophilic addition 393–401
resonance structures 393
dienes, radical addition of HBr 330
esters 396
nitriles 396
systems, electrophilic addition reactions
296–9
Conjugation 37–41
delocalization of electrons 38
via enolate anion 354
Constitutional isomers, definition 56