INDEX
677
Alkaloid
biosynthesis, Mannich-like reactions 371
definition 162
opium 162, 186, 343
tropane 370, 375
tropane, stereochemistry and shape 117
Alkanes, radical chlorination 324
Alkenes
from elimination reaction 207
catalytic hydrogenation 332
electrophilic addition 283–92
of halogens 286–92
of halogens, stereochemistry 287
of hydrogen halides 284–6
hydration 285
radical addition 321
of HBr 328
radical polymerization 331
Alkyl groups
electron-donating effect 127, 321
in alkenes 210
in carbocations 193
Alkyl halides, from nucleophilic substitution
reactions 198
Alkylation
carboxylic acid derivatives 378
electrophilic, in steroid side-chain
biosynthesis 294
of aromatic rings 306–8
diethyl malonate 390
enolate anions 357–60
enamines 367
indole 445
Alkynes
catalytic hydrogenation 333
electrophilic addition 292–4
hydration 293
Allenes, chirality 92
Allopurinol, structure 451
Allose
Fischer projection 104
structure and stereochemistry 465
Allosteric inhibitors, definition 532
Alloxanthine, in allopurinol metabolism 451
Allyl radical 322, 325
Allylic
bromination, N-bromosuccinimide 327
carbocations 194, 216
in electrophilic addition 297
in nature 196
resonance structures 49
halogenation, radical 326
isomerization, in unsaturated fatty acid
metabolism 593
radical 326, 330
Allylisothiocyanate, structure 477
Aloe-emodin anthrone, structure 477
Altrose
Fischer projection 104
structure and stereochemistry 465
Amide anion 169
as base 156
as strong base, enolate anions 358
Amides
acidity 372
from acyl halides 263
basicity 139, 259
from carboxylic acid derivatives 262–7
cyclic see lactams
from esters 263
hydrolysis, acid-catalysed 260
base-catalysed 260
peptides and proteins 261
reduction with complex metal hydrides 269
synthesis, chemical 533
Amidines, basicity 140
Amines
basicity
aliphatic 137
aromatic 141
aromatic, substituted 142
methylation via imines 246
as nucleophile in S N 1 and S N 2 reactions
201
with aldehydes and ketones, enamine
formation 247
with aldehydes and ketones, imine
formation 242–7
in amide formation 262
from reduction of amides 269
Amino acid
sequence determination, peptides, 544
N-terminal, determination 544
Amino acids 499–503
abbreviations, Table 500–1
α-amino acid 499
configurations 81
D and L 106
configurations 499
epimerization during peptide biosynthesis
376
Fischer projections 106
in peptides 499
D-amino acids, in ciclosporin 536
in peptidoglycan 538
degradation during peptide hydrolysis 261,
505
as general acid and base catalysts 517
from hydrolysis of peptides and proteins
261
with ionizable side-chains 502
ionization 501
at pH 7 150
isoelectric point, calculation 160
from nucleophilic substitution reactions 202
pK a values, Table 500–1
pK a values in proteins, Table 503
Strecker synthesis 245
structures, Table 500–1
zwitterions 160, 501
Aminoacyl-AMP
as mixed anhydride 282
in non-ribosomal peptide biosynthesis 535
in ribosomal peptide biosynthesis 533, 557
Aminoacyl-tRNA
binding, inhibitors 558
in ribosomal peptide biosynthesis 533, 557
p-Aminobenzoic acid, in folic acid 275
γ-Aminobutyric acid (GABA), see GABA
Aminocyclitol, definition 493
Aminodiazines, tautomerism 430
Aminoglycoside antibiotics 493
β-Aminoketones, from Mannich reaction 370
6-Aminopenicillanic acid
configurations 82
drawing enantiomer and epimers 86
from hydrolysis of penicillins 266
in semi-synthesis of penicillins 266
stereochemistry and shape 116
Aminopurines, tautomerism 449
Aminopyridines
basicity 418
tautomerism 417
Aminoquinolines 441
Aminosugars 492–7
synthesis 492
Ammonia, bonding molecular orbitals 34
Ammonium cation 34, 169
acidity 136
formal charge 47
Ammonium salts, quaternary, see quaternary
ammonium salts
Amoxicillin, functional groups, 4
AMP, cyclic, see cyclic AMP
Amphoteric compounds
amino acids 159
definition 159
Amphotericin
mode of action 294
structure 256
Ampicillin, semi-synthesis 266
Amygdalin, structure 239
Amylase 485
Amylopectin
as polyacetal 232
structure 484
Amylose
as polyacetal 232
structure 484
Androstenedione, from
dehydroepiandrosterone 355
Angiotensin, structure 532
Angiotensin-converting enzyme (ACE), see
ACE
Anhydrides
ester formation 253
mixed 281
from ATP and bicarbonate 609
in fatty acyl AMP 590
in glycolysis 582
in Krebs cycle 588
reactivity 250
synthesis from acyl halides 251
Aniline, basicity 141
Anionic polymerization 400
Anions 19, 24
and curly arrows 46
cyclopentadienyl, aromaticity 43, 44
methyl, electronic structure 32
as nucleophiles 186
stabilized, as nucleophiles 365
Annulenes
definition 42
aromaticity 42
Anomers
α and β, definition 471
acid-catalysed equilibration 475
common sugars 470
definition 469
glucopyranose 226
Anomeric centre 226
definition 469
esterification in sugars 473
Anomeric effect 227, 474
677
Alkaloid
biosynthesis, Mannich-like reactions 371
definition 162
opium 162, 186, 343
tropane 370, 375
tropane, stereochemistry and shape 117
Alkanes, radical chlorination 324
Alkenes
from elimination reaction 207
catalytic hydrogenation 332
electrophilic addition 283–92
of halogens 286–92
of halogens, stereochemistry 287
of hydrogen halides 284–6
hydration 285
radical addition 321
of HBr 328
radical polymerization 331
Alkyl groups
electron-donating effect 127, 321
in alkenes 210
in carbocations 193
Alkyl halides, from nucleophilic substitution
reactions 198
Alkylation
carboxylic acid derivatives 378
electrophilic, in steroid side-chain
biosynthesis 294
of aromatic rings 306–8
diethyl malonate 390
enolate anions 357–60
enamines 367
indole 445
Alkynes
catalytic hydrogenation 333
electrophilic addition 292–4
hydration 293
Allenes, chirality 92
Allopurinol, structure 451
Allose
Fischer projection 104
structure and stereochemistry 465
Allosteric inhibitors, definition 532
Alloxanthine, in allopurinol metabolism 451
Allyl radical 322, 325
Allylic
bromination, N-bromosuccinimide 327
carbocations 194, 216
in electrophilic addition 297
in nature 196
resonance structures 49
halogenation, radical 326
isomerization, in unsaturated fatty acid
metabolism 593
radical 326, 330
Allylisothiocyanate, structure 477
Aloe-emodin anthrone, structure 477
Altrose
Fischer projection 104
structure and stereochemistry 465
Amide anion 169
as base 156
as strong base, enolate anions 358
Amides
acidity 372
from acyl halides 263
basicity 139, 259
from carboxylic acid derivatives 262–7
cyclic see lactams
from esters 263
hydrolysis, acid-catalysed 260
base-catalysed 260
peptides and proteins 261
reduction with complex metal hydrides 269
synthesis, chemical 533
Amidines, basicity 140
Amines
basicity
aliphatic 137
aromatic 141
aromatic, substituted 142
methylation via imines 246
as nucleophile in S N 1 and S N 2 reactions
201
with aldehydes and ketones, enamine
formation 247
with aldehydes and ketones, imine
formation 242–7
in amide formation 262
from reduction of amides 269
Amino acid
sequence determination, peptides, 544
N-terminal, determination 544
Amino acids 499–503
abbreviations, Table 500–1
α-amino acid 499
configurations 81
D and L 106
configurations 499
epimerization during peptide biosynthesis
376
Fischer projections 106
in peptides 499
D-amino acids, in ciclosporin 536
in peptidoglycan 538
degradation during peptide hydrolysis 261,
505
as general acid and base catalysts 517
from hydrolysis of peptides and proteins
261
with ionizable side-chains 502
ionization 501
at pH 7 150
isoelectric point, calculation 160
from nucleophilic substitution reactions 202
pK a values, Table 500–1
pK a values in proteins, Table 503
Strecker synthesis 245
structures, Table 500–1
zwitterions 160, 501
Aminoacyl-AMP
as mixed anhydride 282
in non-ribosomal peptide biosynthesis 535
in ribosomal peptide biosynthesis 533, 557
Aminoacyl-tRNA
binding, inhibitors 558
in ribosomal peptide biosynthesis 533, 557
p-Aminobenzoic acid, in folic acid 275
γ-Aminobutyric acid (GABA), see GABA
Aminocyclitol, definition 493
Aminodiazines, tautomerism 430
Aminoglycoside antibiotics 493
β-Aminoketones, from Mannich reaction 370
6-Aminopenicillanic acid
configurations 82
drawing enantiomer and epimers 86
from hydrolysis of penicillins 266
in semi-synthesis of penicillins 266
stereochemistry and shape 116
Aminopurines, tautomerism 449
Aminopyridines
basicity 418
tautomerism 417
Aminoquinolines 441
Aminosugars 492–7
synthesis 492
Ammonia, bonding molecular orbitals 34
Ammonium cation 34, 169
acidity 136
formal charge 47
Ammonium salts, quaternary, see quaternary
ammonium salts
Amoxicillin, functional groups, 4
AMP, cyclic, see cyclic AMP
Amphoteric compounds
amino acids 159
definition 159
Amphotericin
mode of action 294
structure 256
Ampicillin, semi-synthesis 266
Amygdalin, structure 239
Amylase 485
Amylopectin
as polyacetal 232
structure 484
Amylose
as polyacetal 232
structure 484
Androstenedione, from
dehydroepiandrosterone 355
Angiotensin, structure 532
Angiotensin-converting enzyme (ACE), see
ACE
Anhydrides
ester formation 253
mixed 281
from ATP and bicarbonate 609
in fatty acyl AMP 590
in glycolysis 582
in Krebs cycle 588
reactivity 250
synthesis from acyl halides 251
Aniline, basicity 141
Anionic polymerization 400
Anions 19, 24
and curly arrows 46
cyclopentadienyl, aromaticity 43, 44
methyl, electronic structure 32
as nucleophiles 186
stabilized, as nucleophiles 365
Annulenes
definition 42
aromaticity 42
Anomers
α and β, definition 471
acid-catalysed equilibration 475
common sugars 470
definition 469
glucopyranose 226
Anomeric centre 226
definition 469
esterification in sugars 473
Anomeric effect 227, 474