INDEX
695
Thioketal
formation 235
as protecting group 235
Thiols
acidity 125
conjugate addition to acrolein 395
as nucleophile
hemithioacetal and hemithioketal
formation 235
in S N 1 and S N 2 reactions 199
thioacetal and thioketal formation 235
thioester formation 261
Thiolane, structure 404
Thiolase, in fatty acid β-oxidation 591
Thionyl chloride, in synthesis of acyl
chlorides 251
Thiophene
dipole 427
molecular structure 426
Thiophene and furan, reactivity 427
Threonine, structure and pK a values 501
Threose, structure and stereochemistry 465
Thymine
formation from uracil 455
hydrogen bonding 51
in nucleic acids 550
pyrimidine structure 431
tautomeric forms 431
Thyroxine, biosynthesis via phenolic oxidative
coupling 344
α-Tocopherol (vitamin E)
as antioxidant 336
regeneration 338
p-Toluenesulfonyl chloride, see tosyl chloride
Tomatidine, as spiro compound 107
Torsional asymmetry 92
gossypol 94
Tosyl chloride (p-toluenesulfonyl chloride)
273
and S N 2 reactions 190
Tosyl esters, see tosylates
Tosylate anion, as leaving group 274, 492
Tosylates
formation 273
in elimination reactions 274
in nucleophilic substitutions 273
in S N2 reactions 189
TPP (thiamine diphosphate)
as carrier of acyl anion equivalents 607
in decarboxylation of pyruvic acid 438
in Krebs cycle 585, 587
structure 437, 605
as thiazolium salt 605
ylid formation 438, 605
TPP-dependent reactions 605–8
trans and cis, see configuration
Transaldolase, imine–enamime mechanism
608
Transaminase 598
Transamination
definition 598
in formation of aminosugars 492
of GABA 602
mechanism 599
Transcriptase, reverse 559
Transcription
definition 556
inhibitors 558
Transesterification
acid-catalysed 254
in action of acetylcholinesterase 279
of COX by aspirin 254
transfer-RNA (tRNA), see RNA
Transimination
mechanism 604
and PLP binding 604
Transition state
definition 173
energy diagram 174
in E2 reactions 207
in S N 2 reactions 183
Transketolase
mechanism 608
reactions catalysed 608
role of TPP 607
Translation
definition 556
inhibitors 558
of mRNA, mechanism 556
Translocation, definition 558
Tricarboxylic acid cycle, see Krebs cycle
Trimethoprim, structure 455
Triose phosphate isomerase
enzyme mechanism 524
in glycolysis 581
Triphenylmethyl, see trityl
Triphosphoric acid, structure 277
Triprolidine, configuration 85
Trityl carbocation
resonance stabilization 194, 567
Trivial names 15
fused heterocycles 438
Tropane alkaloids 370, 375
nitrogen inversion 118
stereochemistry and shape 117
Tropine
configuration 119
as meso compound 375
stereochemistry and shape 117
synthesis via Mannich reaction 370
Trypsin
in peptide sequence determination 546
specificity 521
Tryptophan
hydroxylation 602
as indole derivative 446
instability in acid 261
structure and pK a values 501
Tubocurarine
biosynthesis via phenolic oxidative
coupling 342
structure 202
β-Turn, in proteins 509
Twist-boat conformation
cyclohexane 66
di-tert-butylcyclohexanes 72
Tyrosine
ionization 503
at pH 7 152
structure and pK a values 501
Ubiquinol, in electron transport chain 577
Ubiquinone, in electron transport chain
577
UDPglucose (uridine diphosphoglucose)
in biosynthesis of glucosides 480
oxidation to UDPglucuronic acid 489
structure 480
UDPglucuronic acid (uridine
diphosphoglucuronic acid)
in drug conjugation 489
structure 487
UDPsugars
in biosynthesis oligosaccharides and
polysaccharides 484
in glycoside biosynthesis 480
Unsaturated compounds 30
Uracil
conversion into thymine 455
hydrogen bonding 51
in nucleic acids 550
pyrimidine structure 431
tautomeric forms 431
Uric acid
acidity 451
structure 450
Uridine, structure 550
Uridine diphosphoglucose, see UDPglucose
Uridine diphosphoglucuronic acid, see
UDPglucuronic acid
Uridylic acid, in nucleotide biosynthesis 563
Uronic acid
definition 485
derivatives, natural 488
Valence
electrons 19
shell 19
Valency 1, 19, 46
Valine
epimerization during peptide biosynthesis
377
structure and pK a values 501
Vigabatrin, nomenclature 11
Vinyl cation 292
Viruses, composition 558
Vision, vitamin A 40
Vitamin A 1 , see retinol
Vitamin B 1 , see thiamine
Vitamin B 2 , see riboflavin
Vitamin B 5 , see pantothenic acid
Vitamin B 6 (pyridoxal, pyridoxine,
pyridoxamine) 246, 600
Vitamin B 9 , see folic acid
Vitamin B 12 , structure 425
Vitamin C (ascorbic acid)
acidity 490
as antioxidant 338
biosynthesis 490
structure 490
Vitamin E see α-tocopherol
Vitamin H, see biotin
Wagner–Meerwein rearrangements, see
rearrangement reactions, carbocation
Warfarin, structure and synthesis 420
Water
bonding molecular orbitals 34
695
Thioketal
formation 235
as protecting group 235
Thiols
acidity 125
conjugate addition to acrolein 395
as nucleophile
hemithioacetal and hemithioketal
formation 235
in S N 1 and S N 2 reactions 199
thioacetal and thioketal formation 235
thioester formation 261
Thiolane, structure 404
Thiolase, in fatty acid β-oxidation 591
Thionyl chloride, in synthesis of acyl
chlorides 251
Thiophene
dipole 427
molecular structure 426
Thiophene and furan, reactivity 427
Threonine, structure and pK a values 501
Threose, structure and stereochemistry 465
Thymine
formation from uracil 455
hydrogen bonding 51
in nucleic acids 550
pyrimidine structure 431
tautomeric forms 431
Thyroxine, biosynthesis via phenolic oxidative
coupling 344
α-Tocopherol (vitamin E)
as antioxidant 336
regeneration 338
p-Toluenesulfonyl chloride, see tosyl chloride
Tomatidine, as spiro compound 107
Torsional asymmetry 92
gossypol 94
Tosyl chloride (p-toluenesulfonyl chloride)
273
and S N 2 reactions 190
Tosyl esters, see tosylates
Tosylate anion, as leaving group 274, 492
Tosylates
formation 273
in elimination reactions 274
in nucleophilic substitutions 273
in S N2 reactions 189
TPP (thiamine diphosphate)
as carrier of acyl anion equivalents 607
in decarboxylation of pyruvic acid 438
in Krebs cycle 585, 587
structure 437, 605
as thiazolium salt 605
ylid formation 438, 605
TPP-dependent reactions 605–8
trans and cis, see configuration
Transaldolase, imine–enamime mechanism
608
Transaminase 598
Transamination
definition 598
in formation of aminosugars 492
of GABA 602
mechanism 599
Transcriptase, reverse 559
Transcription
definition 556
inhibitors 558
Transesterification
acid-catalysed 254
in action of acetylcholinesterase 279
of COX by aspirin 254
transfer-RNA (tRNA), see RNA
Transimination
mechanism 604
and PLP binding 604
Transition state
definition 173
energy diagram 174
in E2 reactions 207
in S N 2 reactions 183
Transketolase
mechanism 608
reactions catalysed 608
role of TPP 607
Translation
definition 556
inhibitors 558
of mRNA, mechanism 556
Translocation, definition 558
Tricarboxylic acid cycle, see Krebs cycle
Trimethoprim, structure 455
Triose phosphate isomerase
enzyme mechanism 524
in glycolysis 581
Triphenylmethyl, see trityl
Triphosphoric acid, structure 277
Triprolidine, configuration 85
Trityl carbocation
resonance stabilization 194, 567
Trivial names 15
fused heterocycles 438
Tropane alkaloids 370, 375
nitrogen inversion 118
stereochemistry and shape 117
Tropine
configuration 119
as meso compound 375
stereochemistry and shape 117
synthesis via Mannich reaction 370
Trypsin
in peptide sequence determination 546
specificity 521
Tryptophan
hydroxylation 602
as indole derivative 446
instability in acid 261
structure and pK a values 501
Tubocurarine
biosynthesis via phenolic oxidative
coupling 342
structure 202
β-Turn, in proteins 509
Twist-boat conformation
cyclohexane 66
di-tert-butylcyclohexanes 72
Tyrosine
ionization 503
at pH 7 152
structure and pK a values 501
Ubiquinol, in electron transport chain 577
Ubiquinone, in electron transport chain
577
UDPglucose (uridine diphosphoglucose)
in biosynthesis of glucosides 480
oxidation to UDPglucuronic acid 489
structure 480
UDPglucuronic acid (uridine
diphosphoglucuronic acid)
in drug conjugation 489
structure 487
UDPsugars
in biosynthesis oligosaccharides and
polysaccharides 484
in glycoside biosynthesis 480
Unsaturated compounds 30
Uracil
conversion into thymine 455
hydrogen bonding 51
in nucleic acids 550
pyrimidine structure 431
tautomeric forms 431
Uric acid
acidity 451
structure 450
Uridine, structure 550
Uridine diphosphoglucose, see UDPglucose
Uridine diphosphoglucuronic acid, see
UDPglucuronic acid
Uridylic acid, in nucleotide biosynthesis 563
Uronic acid
definition 485
derivatives, natural 488
Valence
electrons 19
shell 19
Valency 1, 19, 46
Valine
epimerization during peptide biosynthesis
377
structure and pK a values 501
Vigabatrin, nomenclature 11
Vinyl cation 292
Viruses, composition 558
Vision, vitamin A 40
Vitamin A 1 , see retinol
Vitamin B 1 , see thiamine
Vitamin B 2 , see riboflavin
Vitamin B 5 , see pantothenic acid
Vitamin B 6 (pyridoxal, pyridoxine,
pyridoxamine) 246, 600
Vitamin B 9 , see folic acid
Vitamin B 12 , structure 425
Vitamin C (ascorbic acid)
acidity 490
as antioxidant 338
biosynthesis 490
structure 490
Vitamin E see α-tocopherol
Vitamin H, see biotin
Wagner–Meerwein rearrangements, see
rearrangement reactions, carbocation
Warfarin, structure and synthesis 420
Water
bonding molecular orbitals 34