INDEX
691
use of 155–65
water 136
pK b , definition 135
β-Pleated sheet, in proteins 509–10
PLP (pyridoxal 5
-phosphate)
enzyme binding via transimination 604
imine derivative, acidity 600
imine formation 246
PLP-dependent decarboxylation, amino
acids 601–2
PLP-dependent racemization, amino acids
600
PLP-dependent reactions 600–4
stereochemical factors 603
PLP-dependent reverse aldol reaction 603
in transamination 598
Podophyllotoxin, derivative 233
Polarity, bond 35–7, 170
Polarization
of bonds 36
carbonyl group 221
Polyacrylonitrile 401
Polycyclic systems, stereochemistry 106–19
Polyene macrolides 256, 294
Polymerase chain reaction (PCR) 569
Polymeric supports, in peptide synthesis 543
Polymerization
anionic 400
cationic 300
pyrrole 422
radical, of alkenes 331
Poly(methyl cyanoacrylate) (Superglue) 401
Poly(methyl methacrylate) 401
Polypeptide, definition 499
Polysaccharides 484
definition 463
hydrolysis 485
as polyacetals 232
Polystyrene 331
Polytetrafluoroethylene (PTFE) 331
Polythene (polyethylene) 331
Polyvinyl chloride (PVC) 331
Porphin
resonance forms 424
structure 424
Porphobilinogen, in porphyrin ring
biosynthesis 424
Porphyrins 423
general structure 424
Pravastatin, structure 382
Pregnenolone, conversion into progesterone
354
Preproinsulin 507
pro-R, pro-S convention, see configuration
Prochiral
centre 94
centres, citric acid 96
definition 94
pro-R, pro-S convention for prochiral
centres 95
Prochirality 94–8
aconitase and citric acid 96
alcohol dehydrogenase and ethanol 95
Cahn–Ingold–Prelog system 95
in citrate 586
Progesterone
from pregnenolone 354
stereochemistry and shape 113
Proinsulin 507
Proline
as imino acid 499
peptide chain distortion 509
structure and pK a values 501
Pronunciation 16
Propagation step, radical chain reaction 323
Propene, acidity 129
Propiolic acid, acidity 128
Prostaglandins, biosynthesis via COX 254,
339
Protecting group
acetal or ketal 230
benzyl ester 541
BOC (tert-butoxycarbonyl) 541
ketals 268
thioacetal or thioketal 235
cyclic acetals and ketals 481
in nucleic acid synthesis 566
in peptide synthesis 540
Proteins, see also peptides and proteins
binding sites 513
biosynthesis, ribosomal, antibiotic inhibitors
558
definition 499
globular 511
α-helix 511
hydrolysis 261
molecular shape 505–14
β-pleated sheet 509–10
post-translational changes 558
primary, secondary and tertiary structures
505–14
quaternary structure 513
secondary and tertiary interactions 514
secondary transformations 558
tertiary structure, molecular interactions
511–3
β-turn 509
Protic solvents 187
Protons 19, 24, 169
Protonation 24
Protosteryl cation
in biosynthesis of lanosterol 220
in steroid biosynthesis 303
Prunasin, structure 239, 477
Pseudoephedrine, enantiomers 85
Pseudotropine, stereochemistry and shape
119
Psilocin, structure 447
Psilocybin, structure 447
Pteridine, systematic nomenclature 449, 452
Pteridines, structure 452
Purine
acidity 450
basicity 449
systematic nomenclature 448
Purines
bases in DNA 51
in nucleic acids 550
metabolism, uric acid formation 451
nucleotides, biosynthesis 563
structure 449
tautomerism 449
Purpurosamine, in gentamicin 494
Pyranose forms 226, 468
Pyranose and furanose forms, aldohexoses,
equilibrium proportions, Table 470
Pyrazine, see also diazines
basicity 427
structure 427
Pyrazinone, tautomerism 430
Pyrazole
basicity 438
hydrogen bonding 435
structure 432
Pyrethric acid, structure 61
Pyrethrins, general structure 61
Pyrethrolone, structure 61
Pyridazine, see also diazines
basicity 427
structure 427
Pyridazinone, tautomerism 430
Pyridine
aromaticity 44, 405
basicity 143, 408
bond lengths 405
as catalyst in synthesis of anhydrides 251
as catalyst in synthesis of esters 253
Chichibabin reaction 411
dipole 406
electrophilic substitution 409
Frost circle 406
Hantzsch synthesis 458
hydroxypyridine–pyridone tautomerism 416
molecular structure 405
NMR spectrum 406
as nucleophilic catalyst 264
reactivity 407–12
resonance structures 406
Pyridine-N-oxide
electrophilic substitution 410
synthesis 410
Pyridines, methyl, see picolines
Pyridinium salts
formation 408
nucleophilic addition 414
reduction via complex metal hydrides 414
Pyridones
acidity 416
N-alkylation 417
basicity 416
chlorination 417
tautomerism 416
Pyridoxal 246
structure 600
Pyridoxal 5
-phosphate, see PLP
Pyridoxamine 246
structure 600
Pyridoxamine 5
-phosphate
via imine hydrolysis 246
in transamination 599
Pyridoxine (pyridoxol), structure 600
Pyrimethamine, structure 455
Pyrimidine, see also diazines
basicity 427
structure 427
Pyrimidines
bases in DNA 51
bases, in nucleic acids 431, 550
nucleotides, biosynthesis 563
Pyrimidone, tautomerism 430
Pyroglutamic acid, structure 503
Pyrones 418
Pyrophosphatase, hydrolysis of diphosphate
562, 590
691
use of 155–65
water 136
pK b , definition 135
β-Pleated sheet, in proteins 509–10
PLP (pyridoxal 5
-phosphate)
enzyme binding via transimination 604
imine derivative, acidity 600
imine formation 246
PLP-dependent decarboxylation, amino
acids 601–2
PLP-dependent racemization, amino acids
600
PLP-dependent reactions 600–4
stereochemical factors 603
PLP-dependent reverse aldol reaction 603
in transamination 598
Podophyllotoxin, derivative 233
Polarity, bond 35–7, 170
Polarization
of bonds 36
carbonyl group 221
Polyacrylonitrile 401
Polycyclic systems, stereochemistry 106–19
Polyene macrolides 256, 294
Polymerase chain reaction (PCR) 569
Polymeric supports, in peptide synthesis 543
Polymerization
anionic 400
cationic 300
pyrrole 422
radical, of alkenes 331
Poly(methyl cyanoacrylate) (Superglue) 401
Poly(methyl methacrylate) 401
Polypeptide, definition 499
Polysaccharides 484
definition 463
hydrolysis 485
as polyacetals 232
Polystyrene 331
Polytetrafluoroethylene (PTFE) 331
Polythene (polyethylene) 331
Polyvinyl chloride (PVC) 331
Porphin
resonance forms 424
structure 424
Porphobilinogen, in porphyrin ring
biosynthesis 424
Porphyrins 423
general structure 424
Pravastatin, structure 382
Pregnenolone, conversion into progesterone
354
Preproinsulin 507
pro-R, pro-S convention, see configuration
Prochiral
centre 94
centres, citric acid 96
definition 94
pro-R, pro-S convention for prochiral
centres 95
Prochirality 94–8
aconitase and citric acid 96
alcohol dehydrogenase and ethanol 95
Cahn–Ingold–Prelog system 95
in citrate 586
Progesterone
from pregnenolone 354
stereochemistry and shape 113
Proinsulin 507
Proline
as imino acid 499
peptide chain distortion 509
structure and pK a values 501
Pronunciation 16
Propagation step, radical chain reaction 323
Propene, acidity 129
Propiolic acid, acidity 128
Prostaglandins, biosynthesis via COX 254,
339
Protecting group
acetal or ketal 230
benzyl ester 541
BOC (tert-butoxycarbonyl) 541
ketals 268
thioacetal or thioketal 235
cyclic acetals and ketals 481
in nucleic acid synthesis 566
in peptide synthesis 540
Proteins, see also peptides and proteins
binding sites 513
biosynthesis, ribosomal, antibiotic inhibitors
558
definition 499
globular 511
α-helix 511
hydrolysis 261
molecular shape 505–14
β-pleated sheet 509–10
post-translational changes 558
primary, secondary and tertiary structures
505–14
quaternary structure 513
secondary and tertiary interactions 514
secondary transformations 558
tertiary structure, molecular interactions
511–3
β-turn 509
Protic solvents 187
Protons 19, 24, 169
Protonation 24
Protosteryl cation
in biosynthesis of lanosterol 220
in steroid biosynthesis 303
Prunasin, structure 239, 477
Pseudoephedrine, enantiomers 85
Pseudotropine, stereochemistry and shape
119
Psilocin, structure 447
Psilocybin, structure 447
Pteridine, systematic nomenclature 449, 452
Pteridines, structure 452
Purine
acidity 450
basicity 449
systematic nomenclature 448
Purines
bases in DNA 51
in nucleic acids 550
metabolism, uric acid formation 451
nucleotides, biosynthesis 563
structure 449
tautomerism 449
Purpurosamine, in gentamicin 494
Pyranose forms 226, 468
Pyranose and furanose forms, aldohexoses,
equilibrium proportions, Table 470
Pyrazine, see also diazines
basicity 427
structure 427
Pyrazinone, tautomerism 430
Pyrazole
basicity 438
hydrogen bonding 435
structure 432
Pyrethric acid, structure 61
Pyrethrins, general structure 61
Pyrethrolone, structure 61
Pyridazine, see also diazines
basicity 427
structure 427
Pyridazinone, tautomerism 430
Pyridine
aromaticity 44, 405
basicity 143, 408
bond lengths 405
as catalyst in synthesis of anhydrides 251
as catalyst in synthesis of esters 253
Chichibabin reaction 411
dipole 406
electrophilic substitution 409
Frost circle 406
Hantzsch synthesis 458
hydroxypyridine–pyridone tautomerism 416
molecular structure 405
NMR spectrum 406
as nucleophilic catalyst 264
reactivity 407–12
resonance structures 406
Pyridine-N-oxide
electrophilic substitution 410
synthesis 410
Pyridines, methyl, see picolines
Pyridinium salts
formation 408
nucleophilic addition 414
reduction via complex metal hydrides 414
Pyridones
acidity 416
N-alkylation 417
basicity 416
chlorination 417
tautomerism 416
Pyridoxal 246
structure 600
Pyridoxal 5
-phosphate, see PLP
Pyridoxamine 246
structure 600
Pyridoxamine 5
-phosphate
via imine hydrolysis 246
in transamination 599
Pyridoxine (pyridoxol), structure 600
Pyrimethamine, structure 455
Pyrimidine, see also diazines
basicity 427
structure 427
Pyrimidines
bases in DNA 51
bases, in nucleic acids 431, 550
nucleotides, biosynthesis 563
Pyrimidone, tautomerism 430
Pyroglutamic acid, structure 503
Pyrones 418
Pyrophosphatase, hydrolysis of diphosphate
562, 590