676
INDEX
Acidity (compounds) (continued)
guanine 450
histidine 434
hydrogen cyanide 128
hydrogen halides 125
indole 445
malonic acid 144
methanesulfonic acid 129
nitromethane 365
nitrophenols 134
oxalic acid 144
1,3-pentadiene 129
phenols 133
phenylacetic acid 130
phosphoric acid 144, 275
picolines 412
propene 129
propiolic acid 128
purine 450
pyridones 416
pyrrole 421
salicylic acid 133
succinic acid 144
sulfuric acid 144
thioesters 372
thiols 125
uric acid 451
vitamin C (ascorbic acid) 490
Aconitase
in Krebs cycle 586
stereospecificity 96
cis-Aconitate, in Krebs cycle 586
Acrolein, conjugate addition of thiol 395
Acronyms
biochemicals, Table 16
reagents and solvents, Table 16
Acrylic acid, acidity 128
Activation energy, definition 173
Active site, definition 514
ACV, as precursor of β-lactam antibiotics 537
Acyclonucleosides, definition 559
Acyl anion equivalents, TPP as carrier 607
Acyl carrier protein (ACP), in fatty acid
biosynthesis 597
Acyl chlorides
in Friedel–Crafts reactions 308
synthesis 251
Acyl halides
as electrophiles in Claisen reaction 383
ester formation 253
reactivity 250
in synthesis of amides 263
in synthesis of anhydrides 251
Acylation
electrophilic, of aromatic rings 308
of enolate anions, see Claisen reaction
of nucleophiles 248
Acyl-CoA dehydrogenase, in fatty acid
β-oxidation 591
Acyl-CoA synthetase, in fatty acid oxidation
590
Acylium ions, in Friedel–Crafts reactions 308
Acylphosphates, as mixed anhydrides 281
Acylpyridinium ion
as nucleophilic catalyst 264
in synthesis of anhydrides 251
in synthesis of esters 253
Acylpyridinium salts, formation 408
Addition
1,4-addition, see conjugate addition
anti 287
conjugate, see conjugate addition
intramolecular electrophilic 300
radical 321
syn 287
in catalytic hydrogenation 332
Addition reactions 175
to carbonyl group
electrophilic mechanism 221
irreversible 223
nucleophilic mechanism 221
reversible 223
electrophilic, see electrophilic addition
nucleophilic, of carbonyl groups 221–48
radical 328–31
Addition–dehydration, aldol reaction 360–5
Addition–elimination reactions
in imine formation 242
in nucleophilic substitution 248
Adenine
acidity 450
basicity 449
hydrogen bonding 51
metabolism 451
in nucleic acids 550
structure 478
tautomerism 449
Adenosine
as N-glycoside 478
structure 550
triphosphate (ATP), see ATP
S-Adenosylmethionine (SAM)
in biological methylation reactions 199
biosynthesis 200
as nucleoside 560
and regeneration of methionine 454
in sterol methylation reactions 295
Adenylate cyclase, in formation of cyclic
AMP 561
Adenylic acid, structure 549
Adrenaline (epinephrine)
biosynthesis 602
from methylation of noradrenaline 200
nomenclature 12
Aflatoxins 202, 203
Aglycone, definition 474
Agonist, definition 514
Alanine
isoelectric point, calculation 161
structure and pK a values 500
Alcohol dehydrogenase
in glycolysis 584
stereospecificity 95
Alcohols
acidity 125, 127
from aldehydes and ketones
with acetylides 241
with Grignard reagents 240
by reduction 235
basicity 138
from carboxylic acid derivatives and
Grignard reagents 271
hydrogen bonding 50
as nucleophile
in acetal and ketal formation 229
in ester formation 252–6
in hemiacetal and hemiketal formation
224
in S N 1 and S N 2 reactions 198
from reduction of carboxylic acid
derivatives 268
Aldaric acids, definition 486
Aldehydes
acetal formation 229
hemiacetal formation
acid-catalysed 224
base-catalysed 225
hemithioacetal formation 235
nucleophilic addition reactions 221–48
reaction with
acetylides 241
amines 242
cyanide 238
Grignard reagents 240
complex metal hydrides 235
from reduction of carboxylic acid
derivatives 268
thioacetal formation 235
Aldehydes and ketones
aldol reaction 360–5
enolization 347
halogenation 356
hydrogen exchange 351
racemization 352
relative reactivity 222
Aldimine, in PLP-dependent reactions 246,
599
Alditols, definition 473
Aldohexoses, equilibrium proportions
pyranose and furanose forms, Table
470
Aldol, from acetaldehyde 360
Aldol and Claisen reactions, in phenol
biosynthesis 385
Aldol reaction 360–5
in biochemistry 363, 381
citrate synthase 528
involving enolate anions from carboxylic
acid derivatives 379
in glycolytic pathway 363
with indole 445
intramolecular 364
in phenol biosynthesis 385
ring size 364
in Knorr pyrrole synthesis 460
in Krebs cycle 586
mixed/crossed 361
with picolines 412
reverse 361, 363
in glycolysis 581
in Robinson annulation 398
Aldolase
as aldol reaction 363
enamine mechanism 368
enzyme mechanism 525
enzyme active site 526
in glycolysis 581
Aldol-like reactions, with stabilized anions
365
Aldonic acid, definition 485
Aldose
definition 464
structures 465
Alginic acid, structure 488
INDEX
Acidity (compounds) (continued)
guanine 450
histidine 434
hydrogen cyanide 128
hydrogen halides 125
indole 445
malonic acid 144
methanesulfonic acid 129
nitromethane 365
nitrophenols 134
oxalic acid 144
1,3-pentadiene 129
phenols 133
phenylacetic acid 130
phosphoric acid 144, 275
picolines 412
propene 129
propiolic acid 128
purine 450
pyridones 416
pyrrole 421
salicylic acid 133
succinic acid 144
sulfuric acid 144
thioesters 372
thiols 125
uric acid 451
vitamin C (ascorbic acid) 490
Aconitase
in Krebs cycle 586
stereospecificity 96
cis-Aconitate, in Krebs cycle 586
Acrolein, conjugate addition of thiol 395
Acronyms
biochemicals, Table 16
reagents and solvents, Table 16
Acrylic acid, acidity 128
Activation energy, definition 173
Active site, definition 514
ACV, as precursor of β-lactam antibiotics 537
Acyclonucleosides, definition 559
Acyl anion equivalents, TPP as carrier 607
Acyl carrier protein (ACP), in fatty acid
biosynthesis 597
Acyl chlorides
in Friedel–Crafts reactions 308
synthesis 251
Acyl halides
as electrophiles in Claisen reaction 383
ester formation 253
reactivity 250
in synthesis of amides 263
in synthesis of anhydrides 251
Acylation
electrophilic, of aromatic rings 308
of enolate anions, see Claisen reaction
of nucleophiles 248
Acyl-CoA dehydrogenase, in fatty acid
β-oxidation 591
Acyl-CoA synthetase, in fatty acid oxidation
590
Acylium ions, in Friedel–Crafts reactions 308
Acylphosphates, as mixed anhydrides 281
Acylpyridinium ion
as nucleophilic catalyst 264
in synthesis of anhydrides 251
in synthesis of esters 253
Acylpyridinium salts, formation 408
Addition
1,4-addition, see conjugate addition
anti 287
conjugate, see conjugate addition
intramolecular electrophilic 300
radical 321
syn 287
in catalytic hydrogenation 332
Addition reactions 175
to carbonyl group
electrophilic mechanism 221
irreversible 223
nucleophilic mechanism 221
reversible 223
electrophilic, see electrophilic addition
nucleophilic, of carbonyl groups 221–48
radical 328–31
Addition–dehydration, aldol reaction 360–5
Addition–elimination reactions
in imine formation 242
in nucleophilic substitution 248
Adenine
acidity 450
basicity 449
hydrogen bonding 51
metabolism 451
in nucleic acids 550
structure 478
tautomerism 449
Adenosine
as N-glycoside 478
structure 550
triphosphate (ATP), see ATP
S-Adenosylmethionine (SAM)
in biological methylation reactions 199
biosynthesis 200
as nucleoside 560
and regeneration of methionine 454
in sterol methylation reactions 295
Adenylate cyclase, in formation of cyclic
AMP 561
Adenylic acid, structure 549
Adrenaline (epinephrine)
biosynthesis 602
from methylation of noradrenaline 200
nomenclature 12
Aflatoxins 202, 203
Aglycone, definition 474
Agonist, definition 514
Alanine
isoelectric point, calculation 161
structure and pK a values 500
Alcohol dehydrogenase
in glycolysis 584
stereospecificity 95
Alcohols
acidity 125, 127
from aldehydes and ketones
with acetylides 241
with Grignard reagents 240
by reduction 235
basicity 138
from carboxylic acid derivatives and
Grignard reagents 271
hydrogen bonding 50
as nucleophile
in acetal and ketal formation 229
in ester formation 252–6
in hemiacetal and hemiketal formation
224
in S N 1 and S N 2 reactions 198
from reduction of carboxylic acid
derivatives 268
Aldaric acids, definition 486
Aldehydes
acetal formation 229
hemiacetal formation
acid-catalysed 224
base-catalysed 225
hemithioacetal formation 235
nucleophilic addition reactions 221–48
reaction with
acetylides 241
amines 242
cyanide 238
Grignard reagents 240
complex metal hydrides 235
from reduction of carboxylic acid
derivatives 268
thioacetal formation 235
Aldehydes and ketones
aldol reaction 360–5
enolization 347
halogenation 356
hydrogen exchange 351
racemization 352
relative reactivity 222
Aldimine, in PLP-dependent reactions 246,
599
Alditols, definition 473
Aldohexoses, equilibrium proportions
pyranose and furanose forms, Table
470
Aldol, from acetaldehyde 360
Aldol and Claisen reactions, in phenol
biosynthesis 385
Aldol reaction 360–5
in biochemistry 363, 381
citrate synthase 528
involving enolate anions from carboxylic
acid derivatives 379
in glycolytic pathway 363
with indole 445
intramolecular 364
in phenol biosynthesis 385
ring size 364
in Knorr pyrrole synthesis 460
in Krebs cycle 586
mixed/crossed 361
with picolines 412
reverse 361, 363
in glycolysis 581
in Robinson annulation 398
Aldolase
as aldol reaction 363
enamine mechanism 368
enzyme mechanism 525
enzyme active site 526
in glycolysis 581
Aldol-like reactions, with stabilized anions
365
Aldonic acid, definition 485
Aldose
definition 464
structures 465
Alginic acid, structure 488