INDEX
687
enols and enolate anions 351
glucose,
14 C-labelled 465
indole 443
oxazolium and thiazolium salts 437
using bases 157–9
Isoxazole
basicity 438
structure 432
IUPAC (International Union of Pure and
Applied Chemistry)
non-systematic names 15
priority rules (configuration at chiral
centres) 80
priority rules (configuration at double
bonds) 84
systematic nomenclature 6–14
Jasmolone, structure 61
Kekul´ e forms
aromatic rings 2
benzene 44, 45
Ketals
formation 229
as protecting group 230, 268
Ketal and acetal groups in sucrose 231
Ketals and acetals, cyclic, as protecting
groups 481
Ketamine, nomenclature 12
Ketimine, in PLP-dependent reactions 246,
599
Keto–enol tautomerism, see tautomerism
β-Ketoacids
decarboxylation 388
in biochemistry 389
in Krebs cycle 587
β-Ketoesters
acid hydrolysis 387
from Claisen reaction 379
reverse Claisen reaction 387
α-Ketoglutarate, see 2-oxoglutarate
Ketones
from carboxylic acid derivatives and
Grignard reagents 271
hemiketal formation 224
hemithioketal formation 235
from hydration of alkynes 293
ketal formation 229
nucleophilic addition reactions 221–48
reaction with acetylides 241
reaction with amines 242
reaction with cyanide 238
reaction with Grignard reagents 240
reduction with complex metal hydrides 235
thioketal formation 235
Ketones and aldehydes
enolization 347
halogenation 356
hydrogen exchange 351
racemization 352
Ketone–ester condensations, predicting the
product 384
Ketose, definition 464
Kiliani–Fischer synthesis
extending aldose chain 465
in aminosugar synthesis 492
Kinetic control
in addition to conjugated dienes 297
in nucleophilic addition to conjugated
carbonyl derivatives 395
Kinetics, reaction, see reaction kinetics
Knorr pyrrole synthesis 460
Krebs cycle 584–9
aldol reactions 363
citrate synthase mechanism 528
energy yield 589
isocitrate dehydrogenase 389
K w , ionization constant for water 135
temperature dependence 146
Labelling
exchange 158
carboxylic acid derivatives 374
enols and enolate anions 351
hydroxyl groups 158
indole 443
oxazolium and thiazolium salts 437
isotopic, using bases 157–9
Lactams
as cyclic amides 265
nomenclature 265
β-Lactam antibiotics 265
hydrolysis 266
mode of action 539
shape of penicillins 115
structural features 537
β-Lactamases 266
comparison with serine protease 523
mechanism of action 267, 539
Lactase 485
Lactate dehydrogenase, in glycolysis 584
Lactic acid
in glycolysis 584
from stereospecific reduction of pyruvic
acid 238
Lactones
as cyclic esters 255
lactone–hydroxyacid equilibria, Table 255
macrolides 255
nomenclature 255
reduction with sodium borohydride 466
Lactose, structure 483
Lactulose, structure 483
Laevorotatory enantiomer, definition 76
LAH, see lithium aluminium hydride
Lanosterol
biosynthesis, rearrangement reactions 219
in steroid biosynthesis 303
LDA, see lithium diisopropylamide
Leaving groups
and acidity 189, Table 189
definition 171
in carbonyl additions 224
in carboxylic acid derivatives, 249–50
protonation 250
in ester–amide conversion 263
in imine formation 242
linking chemistry of amides and imines 269
and reactivity in carboxylic acid derivatives
249–50, Table 250
in S N 2 reactions 183, 188–90
phosphates and diphosphates 196
tosylate anion 274
Leucine, structure and pK a values 500
Lewis
acids and bases 121
acid, AlH 3 in LAH reductions 235
acids, in electrophilic aromatic substitution
305
acids, in Friedel–Crafts reactions 306
definition of acids and bases 121
structures 20, 45
Lidocaine, nomenclature 14
Lignocaine, see lidocaine
Limiting structures, see resonance structures
Limonene, biosynthesis 303
Linalyl diphosphate 302
allylic cation 107
Linamarin, structure 239
Lindane, conformational isomers 73
Line drawings 1–3, 20, 32
Linear combination of atomic orbitals, see
atomic orbitals
Linoleic acid
autoxidation 335
metabolism 594
structure 259
Lipases
in hydrolysis of fats 590
in resolution of enantiomers 100
Lipoic acid
in Krebs cycle 585, 587
in oxidative decarboxylation 606
Liquiritigenin, synthesis by conjugate addition
396
Lithium aluminium hydride (LAH) 205, 235,
267
addition to conjugated carbonyl derivatives
395
reaction with aldehydes and ketones 235
reaction with water 205, 236
reduction of amides 269
reduction of carboxylic acid derivatives 267
reduction of pyridinium salts 414
in S N 1 and S N 2 reactions 205
Lithium diisopropylamide (LDA)
selective action 360, 362
as strong base in aldol reaction 362
as strong base, enolate anions 359, 381,
383, 392
Littorine
base hydrolysis 376
structure 375
Lone pair electrons 20, 168
ammonia 34
water 34
LSD, see lysergic acid diethylamide
Lycopene
as antioxidant 337
structure 39
Lysergic acid diethylamide (LSD), structure
447
Lysine
ionization 502
at pH 7 152
isoelectric point, calculation 161
structure and pK a values 500
Lyxose, structure and stereochemistry 465
687
enols and enolate anions 351
glucose,
14 C-labelled 465
indole 443
oxazolium and thiazolium salts 437
using bases 157–9
Isoxazole
basicity 438
structure 432
IUPAC (International Union of Pure and
Applied Chemistry)
non-systematic names 15
priority rules (configuration at chiral
centres) 80
priority rules (configuration at double
bonds) 84
systematic nomenclature 6–14
Jasmolone, structure 61
Kekul´ e forms
aromatic rings 2
benzene 44, 45
Ketals
formation 229
as protecting group 230, 268
Ketal and acetal groups in sucrose 231
Ketals and acetals, cyclic, as protecting
groups 481
Ketamine, nomenclature 12
Ketimine, in PLP-dependent reactions 246,
599
Keto–enol tautomerism, see tautomerism
β-Ketoacids
decarboxylation 388
in biochemistry 389
in Krebs cycle 587
β-Ketoesters
acid hydrolysis 387
from Claisen reaction 379
reverse Claisen reaction 387
α-Ketoglutarate, see 2-oxoglutarate
Ketones
from carboxylic acid derivatives and
Grignard reagents 271
hemiketal formation 224
hemithioketal formation 235
from hydration of alkynes 293
ketal formation 229
nucleophilic addition reactions 221–48
reaction with acetylides 241
reaction with amines 242
reaction with cyanide 238
reaction with Grignard reagents 240
reduction with complex metal hydrides 235
thioketal formation 235
Ketones and aldehydes
enolization 347
halogenation 356
hydrogen exchange 351
racemization 352
Ketone–ester condensations, predicting the
product 384
Ketose, definition 464
Kiliani–Fischer synthesis
extending aldose chain 465
in aminosugar synthesis 492
Kinetic control
in addition to conjugated dienes 297
in nucleophilic addition to conjugated
carbonyl derivatives 395
Kinetics, reaction, see reaction kinetics
Knorr pyrrole synthesis 460
Krebs cycle 584–9
aldol reactions 363
citrate synthase mechanism 528
energy yield 589
isocitrate dehydrogenase 389
K w , ionization constant for water 135
temperature dependence 146
Labelling
exchange 158
carboxylic acid derivatives 374
enols and enolate anions 351
hydroxyl groups 158
indole 443
oxazolium and thiazolium salts 437
isotopic, using bases 157–9
Lactams
as cyclic amides 265
nomenclature 265
β-Lactam antibiotics 265
hydrolysis 266
mode of action 539
shape of penicillins 115
structural features 537
β-Lactamases 266
comparison with serine protease 523
mechanism of action 267, 539
Lactase 485
Lactate dehydrogenase, in glycolysis 584
Lactic acid
in glycolysis 584
from stereospecific reduction of pyruvic
acid 238
Lactones
as cyclic esters 255
lactone–hydroxyacid equilibria, Table 255
macrolides 255
nomenclature 255
reduction with sodium borohydride 466
Lactose, structure 483
Lactulose, structure 483
Laevorotatory enantiomer, definition 76
LAH, see lithium aluminium hydride
Lanosterol
biosynthesis, rearrangement reactions 219
in steroid biosynthesis 303
LDA, see lithium diisopropylamide
Leaving groups
and acidity 189, Table 189
definition 171
in carbonyl additions 224
in carboxylic acid derivatives, 249–50
protonation 250
in ester–amide conversion 263
in imine formation 242
linking chemistry of amides and imines 269
and reactivity in carboxylic acid derivatives
249–50, Table 250
in S N 2 reactions 183, 188–90
phosphates and diphosphates 196
tosylate anion 274
Leucine, structure and pK a values 500
Lewis
acids and bases 121
acid, AlH 3 in LAH reductions 235
acids, in electrophilic aromatic substitution
305
acids, in Friedel–Crafts reactions 306
definition of acids and bases 121
structures 20, 45
Lidocaine, nomenclature 14
Lignocaine, see lidocaine
Limiting structures, see resonance structures
Limonene, biosynthesis 303
Linalyl diphosphate 302
allylic cation 107
Linamarin, structure 239
Lindane, conformational isomers 73
Line drawings 1–3, 20, 32
Linear combination of atomic orbitals, see
atomic orbitals
Linoleic acid
autoxidation 335
metabolism 594
structure 259
Lipases
in hydrolysis of fats 590
in resolution of enantiomers 100
Lipoic acid
in Krebs cycle 585, 587
in oxidative decarboxylation 606
Liquiritigenin, synthesis by conjugate addition
396
Lithium aluminium hydride (LAH) 205, 235,
267
addition to conjugated carbonyl derivatives
395
reaction with aldehydes and ketones 235
reaction with water 205, 236
reduction of amides 269
reduction of carboxylic acid derivatives 267
reduction of pyridinium salts 414
in S N 1 and S N 2 reactions 205
Lithium diisopropylamide (LDA)
selective action 360, 362
as strong base in aldol reaction 362
as strong base, enolate anions 359, 381,
383, 392
Littorine
base hydrolysis 376
structure 375
Lone pair electrons 20, 168
ammonia 34
water 34
LSD, see lysergic acid diethylamide
Lycopene
as antioxidant 337
structure 39
Lysergic acid diethylamide (LSD), structure
447
Lysine
ionization 502
at pH 7 152
isoelectric point, calculation 161
structure and pK a values 500
Lyxose, structure and stereochemistry 465