INDEX
693
Riboflavin (vitamin B2), structure 456
Ribofuranose 227, 469
anomeric forms 227
Ribonucleic acid, see RNA
Ribopyranose 469
Ribose
biologically important derivatives 228
hemiacetal form 227
from Fischer projection 105
structure 471
in RNA 550
ribofuranose forms 469
ribopyranose forms 469
structure and stereochemistry 464, 465
Ribosomal peptide biosynthesis 533
antibiotic inhibitors 558
ribosomal-RNA (rRNA), see RNA
Ribosome 556
Ribulose, structure and stereochemistry 464
Ring currents
and aromaticity 44
pyridine 406
Ring size,
in intramolecular aldol reaction 364
in intramolecular Claisen reaction 382
Ring strain 60
cycloalkanes, Table 63
cyclobutane 60
cyclopentane 62
cyclopropane 60
in rearrangement reactions 217
Rivastigmine, as acetylcholinesterase inhibitor
279
Rizatriptan, structure 447
RNA (ribonucleic acid) 50, 228, 555
base pairing 432
phosphodiesters in 276
pyrimidines 431
mRNA (messenger RNA) 555
synthesis 556
rRNA (ribosomal RNA) 555
in ribosome 556
tRNA (transfer RNA) 555
in ribosomal peptide biosynthesis 533
in translation 556
RNA polymerase, in RNA synthesis 556
Robinson annulation 398
Salicin
structure 476
synthesis 479
Salicyl alcohol, structure 476
Salicylic acid
acidity 133
methylation to methyl salicylate 200
Salsolinol, synthesis 371
Salt solutions, pH calculation 148
SAM, see S-adenosylmethionine
Sanger reagent (2,4-dinitrofluorobenzene)
N-terminal amino acid determination 544
Saponification, definition 259
Sarcosine (N-methylglycine), structure 503
Sarin, as acetylcholinesterase inhibitor 280
Saturated compounds 30
Sawhorse representation
butane 58
definition 57
ethane 57
Saytzeff elimination 209
Schiff base, see imine
Schr¨ odinger wave equation 20
Scopine, stereochemistry and shape 117
Serine, structure and pK a values 501
Serine esterase 519
Serine hydrolase 519
Serine protease 521
cleavage sites 521
Serotonin, see 5-hydroxytryptamine
Shells 20
filled 23
valence 19
Side-chains, in steroids 294
Sigma (σ) bonds, see bonds, sigma
Sinigrin, structure 477
Sitosterol, in plants 294
Skraup quinoline synthesis 458
S N 1 reactions 191–8
biological 196
in cyclic systems 195
energy diagram 192
mechanism 191
rate of reaction 191
rate-determining step 191
solvent effects 195
effect of substituents 193, Table 193
S N 2 reactions 183–91
in cyclic systems 190
energy diagram 184
leaving groups 188–90
mechanism 183
nucleophiles 185
racemization 184
rate of reaction 183
rate-determining step 183
selective alkylation of morphine 186
solvent effects 187
effect of substituents 184, Table 185
transition state 183
variables in rate of reaction 184
S N 1 and SN2 reactions
acetylides as nucleophile 205
amines as nucleophile 201
cyanide as nucleophile 204
Grignard reagents as nucleophile 204
halide as nucleophile 198
hydride as nucleophile 205
intramolecular 206
thiols as nucleophile 199
water and alcohols as nucleophile 198
S N 1 or S N 2 reactions, according to substrate
195
S N 2
mechanism, in opium alkaloid
biosynthesis 343
S N Ar mechanism 544
Sodium amide
in Chichibabin reaction 411
as strong base, enolate anions 358, 381, 392
Sodium borohydride 205, 235, 267
addition to conjugated carbonyl derivatives
395
cleavage of disulfide bridges 506
reduction
of aldehydes and ketones 235
of carboxylic acid derivatives 267
of hexoses 473
of lactones 466
of pyridinium salts 414
Sodium tert-butoxide, as base 157
Sodium cyanoborohydride, reduction of
imines 246
Sodium hydride
as base 157
as strong base, enolate anions 358, 381, 392
Solasodine, as spiro compound 107
Solid phase
nucleic acid synthesis 566
peptide synthesis 543
Solvents
aprotic polar, Table 188
protic 187
Solvent effects
S N 1 reactions 195
S N 2 reactions 187
Sorbitol (glucitol), structure 473
Specific rotation 76
Spectra
absorption 25
atomic 22
emission 25
infra-red, pyridones 416
NMR
aromatics 44
cyclohexane 64
pyridine 406
UV absorption 38
Spiramycin, structure 494
Spiro compounds 106
chirality 93
natural 107
Spiroketal, in diosgenin 107
Squalene
in biosynthesis of lanosterol 219
in steroid biosynthesis 303
Squalene oxide, in steroid biosynthesis 303
Staggered conformation, see conformation
Standard free energy change 173
Starch
constitution 484
as polyacetal 232
Statins, inhibitors of HMG-CoA reductase 382
Stearic acid
energy yield 592
structure 259
Stereochemistry
definition 55
polycyclic systems 106–19
radical reactions 325
Stereodrawings
manipulation 75
Newman projection 57
sawhorse 57
wedge–dot 32, 55
Stereogenic centre 73
Stereoisomers, definition 56
Stereospecificity, enzyme 96
Steroids
biosynthesis 303
biosynthesis, electrophilic additions 300
side-chain biosynthesis 294
progesterone and pregnenolone 354
stereochemistry and shape 112–15
synthesis, via Robinson annulation 398
693
Riboflavin (vitamin B2), structure 456
Ribofuranose 227, 469
anomeric forms 227
Ribonucleic acid, see RNA
Ribopyranose 469
Ribose
biologically important derivatives 228
hemiacetal form 227
from Fischer projection 105
structure 471
in RNA 550
ribofuranose forms 469
ribopyranose forms 469
structure and stereochemistry 464, 465
Ribosomal peptide biosynthesis 533
antibiotic inhibitors 558
ribosomal-RNA (rRNA), see RNA
Ribosome 556
Ribulose, structure and stereochemistry 464
Ring currents
and aromaticity 44
pyridine 406
Ring size,
in intramolecular aldol reaction 364
in intramolecular Claisen reaction 382
Ring strain 60
cycloalkanes, Table 63
cyclobutane 60
cyclopentane 62
cyclopropane 60
in rearrangement reactions 217
Rivastigmine, as acetylcholinesterase inhibitor
279
Rizatriptan, structure 447
RNA (ribonucleic acid) 50, 228, 555
base pairing 432
phosphodiesters in 276
pyrimidines 431
mRNA (messenger RNA) 555
synthesis 556
rRNA (ribosomal RNA) 555
in ribosome 556
tRNA (transfer RNA) 555
in ribosomal peptide biosynthesis 533
in translation 556
RNA polymerase, in RNA synthesis 556
Robinson annulation 398
Salicin
structure 476
synthesis 479
Salicyl alcohol, structure 476
Salicylic acid
acidity 133
methylation to methyl salicylate 200
Salsolinol, synthesis 371
Salt solutions, pH calculation 148
SAM, see S-adenosylmethionine
Sanger reagent (2,4-dinitrofluorobenzene)
N-terminal amino acid determination 544
Saponification, definition 259
Sarcosine (N-methylglycine), structure 503
Sarin, as acetylcholinesterase inhibitor 280
Saturated compounds 30
Sawhorse representation
butane 58
definition 57
ethane 57
Saytzeff elimination 209
Schiff base, see imine
Schr¨ odinger wave equation 20
Scopine, stereochemistry and shape 117
Serine, structure and pK a values 501
Serine esterase 519
Serine hydrolase 519
Serine protease 521
cleavage sites 521
Serotonin, see 5-hydroxytryptamine
Shells 20
filled 23
valence 19
Side-chains, in steroids 294
Sigma (σ) bonds, see bonds, sigma
Sinigrin, structure 477
Sitosterol, in plants 294
Skraup quinoline synthesis 458
S N 1 reactions 191–8
biological 196
in cyclic systems 195
energy diagram 192
mechanism 191
rate of reaction 191
rate-determining step 191
solvent effects 195
effect of substituents 193, Table 193
S N 2 reactions 183–91
in cyclic systems 190
energy diagram 184
leaving groups 188–90
mechanism 183
nucleophiles 185
racemization 184
rate of reaction 183
rate-determining step 183
selective alkylation of morphine 186
solvent effects 187
effect of substituents 184, Table 185
transition state 183
variables in rate of reaction 184
S N 1 and SN2 reactions
acetylides as nucleophile 205
amines as nucleophile 201
cyanide as nucleophile 204
Grignard reagents as nucleophile 204
halide as nucleophile 198
hydride as nucleophile 205
intramolecular 206
thiols as nucleophile 199
water and alcohols as nucleophile 198
S N 1 or S N 2 reactions, according to substrate
195
S N 2
mechanism, in opium alkaloid
biosynthesis 343
S N Ar mechanism 544
Sodium amide
in Chichibabin reaction 411
as strong base, enolate anions 358, 381, 392
Sodium borohydride 205, 235, 267
addition to conjugated carbonyl derivatives
395
cleavage of disulfide bridges 506
reduction
of aldehydes and ketones 235
of carboxylic acid derivatives 267
of hexoses 473
of lactones 466
of pyridinium salts 414
Sodium tert-butoxide, as base 157
Sodium cyanoborohydride, reduction of
imines 246
Sodium hydride
as base 157
as strong base, enolate anions 358, 381, 392
Solasodine, as spiro compound 107
Solid phase
nucleic acid synthesis 566
peptide synthesis 543
Solvents
aprotic polar, Table 188
protic 187
Solvent effects
S N 1 reactions 195
S N 2 reactions 187
Sorbitol (glucitol), structure 473
Specific rotation 76
Spectra
absorption 25
atomic 22
emission 25
infra-red, pyridones 416
NMR
aromatics 44
cyclohexane 64
pyridine 406
UV absorption 38
Spiramycin, structure 494
Spiro compounds 106
chirality 93
natural 107
Spiroketal, in diosgenin 107
Squalene
in biosynthesis of lanosterol 219
in steroid biosynthesis 303
Squalene oxide, in steroid biosynthesis 303
Staggered conformation, see conformation
Standard free energy change 173
Starch
constitution 484
as polyacetal 232
Statins, inhibitors of HMG-CoA reductase 382
Stearic acid
energy yield 592
structure 259
Stereochemistry
definition 55
polycyclic systems 106–19
radical reactions 325
Stereodrawings
manipulation 75
Newman projection 57
sawhorse 57
wedge–dot 32, 55
Stereogenic centre 73
Stereoisomers, definition 56
Stereospecificity, enzyme 96
Steroids
biosynthesis 303
biosynthesis, electrophilic additions 300
side-chain biosynthesis 294
progesterone and pregnenolone 354
stereochemistry and shape 112–15
synthesis, via Robinson annulation 398