694
INDEX
Sterols, in membranes 294
Stigmasterol, in plants 294
Strecker synthesis, of amino acids 245
Streptamine, structure 493
Streptomycin, structure 493
Streptose, in streptomycin 493
Structural isomers, definition 56
Strychnine, in resolution of enantiomers 99
Substituents
directing effects in electrophilic aromatic
substitution, Table 310
effect on S N 1 reactions 193
effect on S N 2 reactions 184
Substitution reactions 175
electrophilic aromatic, see electrophilic
aromatic substitution
nucleophilic 198–206
nucleophilic, of carboxylic acid derivatives
248–72
nucleophilic aromatic, see nucleophilic
aromatic substitution
nucleophilic, bimolecular see S N 2 reactions
nucleophilic, unimolecular see S N 1
reactions
radical 322–8
Substitution or elimination reaction, according
to conditions 214
Substrate-level phosphorylation
in glycolysis 582, 583
in Krebs cycle 588
Succinate dehydrogenase, in Krebs cycle 588
Succinic acid
acidity 144
from GABA 602
in Krebs cycle 588
Succinyl-CoA, in Krebs cycle 587
Succinyl-CoA synthetase, in Krebs cycle 588
Succinyl phosphate, as mixed anhydride 281
Sucrose
acetal and ketal groups 231
hydrolysis 231
structure 483
Sugar, invert 231
Sugars
anomeric forms of common sugars 470
cyclic hemiacetals, conformation 472
D and L 103, 464
definition 463
as hemiacetals or hemiketals 226
hemiacetal forms from Fischer projections
104, 468
Sulfa drugs 274
Sulfanilamide
acidity 274
as enzyme inhibitor 531
synthesis 274
and tetrahydrofolic acid biosynthesis 455
Sulfonamides
as antibiotics 274
as diuretics 275
Sulfonation, of aromatic rings 305
Sulfonic acids 273
from aromatic sulfonation 306
derivatives, comparison with carboxylic
acid derivatives, Table 273
Sulforaphane, structure 477
Sulfur trioxide, in aromatic sulfonation
305
Sulfuric acid
acidity 144
derivatives, nucleophilic substitution
reactions 272–5
esters 272
Sumatriptan, structure 447
Superglue 401
Suxamethonium, structure 202, 211
Symmetry
in achiral molecules 74, 88, 90, 91
in bornane 117
in decalins 109
in Fischer projections 102
in hydrindanes 110
in tropine and scopine 118
syn
addition, definition 287
addition, in catalytic hydrogenation
332
Talose
Fischer projection 104
structure and stereochemistry 465
Tamoxifen
configuration 84
synthesis 213
Tartaric acid
Fischer projections 102
in resolution of enantiomers 99
stereoisomers 90
meso-tartaric acid
Fischer projections 102
structure 90
Tautomer, definition 347
Tautomerism
adenine 449
aminodiazines 430
aminopurines 449
aminopyridines 417
cytosine 431
definition 347
in glycolytic pathway 350
guanine 449
histidine 433
in hydration of alkynes 294
hydroxydiazines 429
hydroxyimine–amide 244
imidazoles 433, 517
imine–enamine, in transamination
599
keto–enol 341, 347
equilibria, Table 348
acid-catalysed 348
base-catalysed 349
in glycolysis 580, 581, 584
purines 449
pyridones 416
thymine 431
uracil 431
Termination step, radical chain reaction 323
C- and N-Terminus, peptides, definition 504
Terpenoid biosynthesis, electrophilic additions
300
α-Terpineol, biosynthesis 303
Testosterone, structure 398
Tetracycline, structure 385
Tetrahydrofolic acid (FH 4 )
structure 453
derivatives 453
Tetrahydrofuran
conformation 72
dipole 427
structure 404
Tetrahydroisoquinoline
alkaloids, biosynthesis 371
Pictet–Spengler synthesis 460
Tetrahydropyran
conformation 72
structure 404
Tetrahydrothiophene
dipole 427
structure 404
Tetrahydrothiopyran, structure 404
Tetrazole, in nucleotide coupling 568
Thalidomide, mutagenic activity of
enantiomers 79
Thebaine
in morphine biosynthesis 343
in opium 343
Theobromine, structure 451
Theophylline
and cyclic AMP 562
structure 451
Thermodynamic control
in addition to conjugated dienes 297
in nucleophilic addition to conjugated
carbonyl derivatives 395
Thiamine (vitamin B 1 ) 437
structure 605
Thiamine diphosphate (TPP), see TPP
Thiazole
basicity 433
reactivity 432
ring, in thiamine 605
structure 432
Thiazolium salts
in TPP 438
hydrogen exchange 437
Thiazolium ylid
from TPP 438
in decarboxylation of pyruvic acid 438
Thietane, structure 404
Thiinane, structure 404
Thiirane, structure 404
Thioacetal
formation 235
as protecting group 235
Thioacids
from carboxylic acid derivatives 261
reactivity 250
Thioacids and thioesters, basicity 140
Thioesters
acidity 372
from carboxylic acid derivatives 261
enzyme-bound, and fatty acid synthase
595
in enzyme binding 516, 530
in glycolysis 582
in non-ribosomal peptide biosynthesis 535
reactivity 250
Thioesterase, in non-ribosomal peptide
biosynthesis 535
Thioethers, from nucleophilic substitution
reactions 199
INDEX
Sterols, in membranes 294
Stigmasterol, in plants 294
Strecker synthesis, of amino acids 245
Streptamine, structure 493
Streptomycin, structure 493
Streptose, in streptomycin 493
Structural isomers, definition 56
Strychnine, in resolution of enantiomers 99
Substituents
directing effects in electrophilic aromatic
substitution, Table 310
effect on S N 1 reactions 193
effect on S N 2 reactions 184
Substitution reactions 175
electrophilic aromatic, see electrophilic
aromatic substitution
nucleophilic 198–206
nucleophilic, of carboxylic acid derivatives
248–72
nucleophilic aromatic, see nucleophilic
aromatic substitution
nucleophilic, bimolecular see S N 2 reactions
nucleophilic, unimolecular see S N 1
reactions
radical 322–8
Substitution or elimination reaction, according
to conditions 214
Substrate-level phosphorylation
in glycolysis 582, 583
in Krebs cycle 588
Succinate dehydrogenase, in Krebs cycle 588
Succinic acid
acidity 144
from GABA 602
in Krebs cycle 588
Succinyl-CoA, in Krebs cycle 587
Succinyl-CoA synthetase, in Krebs cycle 588
Succinyl phosphate, as mixed anhydride 281
Sucrose
acetal and ketal groups 231
hydrolysis 231
structure 483
Sugar, invert 231
Sugars
anomeric forms of common sugars 470
cyclic hemiacetals, conformation 472
D and L 103, 464
definition 463
as hemiacetals or hemiketals 226
hemiacetal forms from Fischer projections
104, 468
Sulfa drugs 274
Sulfanilamide
acidity 274
as enzyme inhibitor 531
synthesis 274
and tetrahydrofolic acid biosynthesis 455
Sulfonamides
as antibiotics 274
as diuretics 275
Sulfonation, of aromatic rings 305
Sulfonic acids 273
from aromatic sulfonation 306
derivatives, comparison with carboxylic
acid derivatives, Table 273
Sulforaphane, structure 477
Sulfur trioxide, in aromatic sulfonation
305
Sulfuric acid
acidity 144
derivatives, nucleophilic substitution
reactions 272–5
esters 272
Sumatriptan, structure 447
Superglue 401
Suxamethonium, structure 202, 211
Symmetry
in achiral molecules 74, 88, 90, 91
in bornane 117
in decalins 109
in Fischer projections 102
in hydrindanes 110
in tropine and scopine 118
syn
addition, definition 287
addition, in catalytic hydrogenation
332
Talose
Fischer projection 104
structure and stereochemistry 465
Tamoxifen
configuration 84
synthesis 213
Tartaric acid
Fischer projections 102
in resolution of enantiomers 99
stereoisomers 90
meso-tartaric acid
Fischer projections 102
structure 90
Tautomer, definition 347
Tautomerism
adenine 449
aminodiazines 430
aminopurines 449
aminopyridines 417
cytosine 431
definition 347
in glycolytic pathway 350
guanine 449
histidine 433
in hydration of alkynes 294
hydroxydiazines 429
hydroxyimine–amide 244
imidazoles 433, 517
imine–enamine, in transamination
599
keto–enol 341, 347
equilibria, Table 348
acid-catalysed 348
base-catalysed 349
in glycolysis 580, 581, 584
purines 449
pyridones 416
thymine 431
uracil 431
Termination step, radical chain reaction 323
C- and N-Terminus, peptides, definition 504
Terpenoid biosynthesis, electrophilic additions
300
α-Terpineol, biosynthesis 303
Testosterone, structure 398
Tetracycline, structure 385
Tetrahydrofolic acid (FH 4 )
structure 453
derivatives 453
Tetrahydrofuran
conformation 72
dipole 427
structure 404
Tetrahydroisoquinoline
alkaloids, biosynthesis 371
Pictet–Spengler synthesis 460
Tetrahydropyran
conformation 72
structure 404
Tetrahydrothiophene
dipole 427
structure 404
Tetrahydrothiopyran, structure 404
Tetrazole, in nucleotide coupling 568
Thalidomide, mutagenic activity of
enantiomers 79
Thebaine
in morphine biosynthesis 343
in opium 343
Theobromine, structure 451
Theophylline
and cyclic AMP 562
structure 451
Thermodynamic control
in addition to conjugated dienes 297
in nucleophilic addition to conjugated
carbonyl derivatives 395
Thiamine (vitamin B 1 ) 437
structure 605
Thiamine diphosphate (TPP), see TPP
Thiazole
basicity 433
reactivity 432
ring, in thiamine 605
structure 432
Thiazolium salts
in TPP 438
hydrogen exchange 437
Thiazolium ylid
from TPP 438
in decarboxylation of pyruvic acid 438
Thietane, structure 404
Thiinane, structure 404
Thiirane, structure 404
Thioacetal
formation 235
as protecting group 235
Thioacids
from carboxylic acid derivatives 261
reactivity 250
Thioacids and thioesters, basicity 140
Thioesters
acidity 372
from carboxylic acid derivatives 261
enzyme-bound, and fatty acid synthase
595
in enzyme binding 516, 530
in glycolysis 582
in non-ribosomal peptide biosynthesis 535
reactivity 250
Thioesterase, in non-ribosomal peptide
biosynthesis 535
Thioethers, from nucleophilic substitution
reactions 199