688
INDEX
Macrolide,
antibiotics 494
definition 255
polyene 256, 294
Malate, in Krebs cycle 589
Malate dehydrogenase, in Krebs cycle 589
Malathion, as acetylcholinesterase inhibitor
280
Maleic acid, as enzyme inhibitor 531
Malonic acid, acidity 144
Malonyl-CoA
Claisen reactions in nature 392
from carboxylation of acetyl-CoA 595,
609
Maltase 485
Maltose, structure 583
Mandelonitrile, structure 477
Mannich reaction 369–72
general 370
synthesis of tropine 370
with pyrrole 422
with indole 445
Mannitol, structure 473
Mannosamine, synthesis 492
Mannose
Fischer projection 104
hemiacetal form, structure 471
from isomerization of glucose 467
structure and stereochemistry 465
Mannuronic acid, in alginates 488
Markovnikov addition, electrophilic addition
of HBr to alkenes 329
Markovnikov rule, in electrophilic addition
reactions 286
Mechanism
overview 167–75
common mistakes 176–81
Melatonin, structure 447
Menthol
conformational isomers 70
nomenclature 12
Mercaptoethanol, in location of disulfide
bridges 506
messenger-RNA (mRNA), see RNA
Meso compounds 90–2
definition 90
Mesomers, see resonance structures
Mesomeric effect, see resonance effect
Mesyl chloride (methanesulfonyl chloride)
273
and S N 2 reactions 190
Mesylate esters, in S N 2 reactions 189
Metabolism, intermediary, definition 573
Methane, bonding molecular orbitals 27
Methanesulfonic acid, acidity 129
Methanesulfonyl chloride, see mesyl chloride
Methanimine, bonding molecular orbitals 35
Methicillin, semi-synthesis 266
Methicillin-resistant Staphylococcus aureus,
see MRSA
Methionine
regeneration from homocysteine 454
structure and pK a values 501
synthesis 395
Methotrexate, structure 455
Methyl
anion, electronic structure 32
formal charge 47
carbocation, electronic structure 32
radical, electronic structure 33
Methyl cyanoacrylate, polymerization 401
Methylcyclohexane
conformational isomers 67
energy difference 67
Newman projections 67
Methylecgonine, stereochemistry and shape
118
Methylenedioxy group, as acetal 233
N-Methylglycine (sarcosine), structure 503
N-Methyl-leucine, structure 503
Methyltransferases 200
N-Methyltyrosine, structure 503
Mevalonic acid
biosynthesis 381
as precursor of cholesterol 381
Michael acceptors, as carcinogens 399
Michael reaction 397–400
in dicoumarol formation 419
in Hantzsch pyridine synthesis 458
with indole 445
in Robinson annulation 398
in Skraup quinoline synthesis 459
in warfarin synthesis 420
Mineralocorticoids, function 291
Mixed aldol reaction, see aldol reaction
Mixed anhydride, see anhydride
Mixed Claisen reaction, see Claisen reaction
Models, molecular 51–3
Module
in non-ribosomal peptide biosynthesis 535
in penicillin biosynthesis 538
Molecular models 51–3
ball-and-stick 52
framework 52
space-filling 52
Molecular orbitals 24–35
acetylene 31
ammonia 34
antibonding 24
benzene, antibonding 42
bonding 42
bonding 24
1,3-butadiene, antibonding 38
bonding 38
ethane 28
ethylene 29
Frost circles 43
hydrogen molecule, antibonding 24
bonding 24
methane 27
1,3-pentadiene 37
1,4-pentadiene 37
σ bond 25
π bond 25
in ethylene 29
in acetylene 31
water 34
Molecular rearrangement, see rearrangement
reactions
Molecular representations 1–3
Molecularity, definition 173
Mono-oxygenase, cytochrome
P-450-dependent, see cytochrome P-450
Monosaccharides 463–73
definition 463
Monoterpenes, interconversion through
enolization 353
Morphine
biosynthesis via phenolic oxidative
coupling 343
functional groups, 4
O-glucuronides 489
ionization 163
isoelectric point 163
receptors 514
selective alkylation 186
shape 515
structure 62
Morpholine
conformation 72
structure 404
MRSA (methicillin-resistant Staphylococcus
aureus) 266
Mucopolysaccharide, definition 496
Muscarine, structure 413
Muscarinic acetylcholine receptors 413
Mutarotation, glucose 226
Mycaminose, in spiramycin 494
Mycarose, in spiramycin 494
Mycophenolic acid, structure 385
Mycosamine, in amphotericin 256
NAD + (nicotinamide adenine dinucleotide)
enantiotopic faces 98
as oxidizing agent 237
as pyridinium salt 413, 415
reduction 415
structure 413
NAD
+ and NADP
+
in biological oxidations 576
as nucleotides 560
NADH (reduced nicotinamide adenine
dinucleotide)
as reducing agent 237
from reduction of NAD + 415
in reduction of pyruvic acid 97
prochiral centre 98
NADH and NADPH
in biological reductions 576
as nucleotides 560
NADP
+ (nicotinamide adenine dinucleotide
phosphate)
as pyridinium salt 413
reduction 415
structure 413
NADPH (reduced nicotinamide adenine
dinucleotide phosphate)
as reducing agent 237
Nalbuphine, structure 62
Nalidixic acid, structure 442
Naltrexone, structure 62
Naphthalene
aromaticity 44
electrophilic aromatic substitution 316
Naratriptan, structure 447
NBS, see N-Bromosuccinimide
Neoisomenthol, conformational isomers 70
Neostigmine, as acetylcholinesterase inhibitor
279
Neryl diphosphate 302
allylic cation 197
INDEX
Macrolide,
antibiotics 494
definition 255
polyene 256, 294
Malate, in Krebs cycle 589
Malate dehydrogenase, in Krebs cycle 589
Malathion, as acetylcholinesterase inhibitor
280
Maleic acid, as enzyme inhibitor 531
Malonic acid, acidity 144
Malonyl-CoA
Claisen reactions in nature 392
from carboxylation of acetyl-CoA 595,
609
Maltase 485
Maltose, structure 583
Mandelonitrile, structure 477
Mannich reaction 369–72
general 370
synthesis of tropine 370
with pyrrole 422
with indole 445
Mannitol, structure 473
Mannosamine, synthesis 492
Mannose
Fischer projection 104
hemiacetal form, structure 471
from isomerization of glucose 467
structure and stereochemistry 465
Mannuronic acid, in alginates 488
Markovnikov addition, electrophilic addition
of HBr to alkenes 329
Markovnikov rule, in electrophilic addition
reactions 286
Mechanism
overview 167–75
common mistakes 176–81
Melatonin, structure 447
Menthol
conformational isomers 70
nomenclature 12
Mercaptoethanol, in location of disulfide
bridges 506
messenger-RNA (mRNA), see RNA
Meso compounds 90–2
definition 90
Mesomers, see resonance structures
Mesomeric effect, see resonance effect
Mesyl chloride (methanesulfonyl chloride)
273
and S N 2 reactions 190
Mesylate esters, in S N 2 reactions 189
Metabolism, intermediary, definition 573
Methane, bonding molecular orbitals 27
Methanesulfonic acid, acidity 129
Methanesulfonyl chloride, see mesyl chloride
Methanimine, bonding molecular orbitals 35
Methicillin, semi-synthesis 266
Methicillin-resistant Staphylococcus aureus,
see MRSA
Methionine
regeneration from homocysteine 454
structure and pK a values 501
synthesis 395
Methotrexate, structure 455
Methyl
anion, electronic structure 32
formal charge 47
carbocation, electronic structure 32
radical, electronic structure 33
Methyl cyanoacrylate, polymerization 401
Methylcyclohexane
conformational isomers 67
energy difference 67
Newman projections 67
Methylecgonine, stereochemistry and shape
118
Methylenedioxy group, as acetal 233
N-Methylglycine (sarcosine), structure 503
N-Methyl-leucine, structure 503
Methyltransferases 200
N-Methyltyrosine, structure 503
Mevalonic acid
biosynthesis 381
as precursor of cholesterol 381
Michael acceptors, as carcinogens 399
Michael reaction 397–400
in dicoumarol formation 419
in Hantzsch pyridine synthesis 458
with indole 445
in Robinson annulation 398
in Skraup quinoline synthesis 459
in warfarin synthesis 420
Mineralocorticoids, function 291
Mixed aldol reaction, see aldol reaction
Mixed anhydride, see anhydride
Mixed Claisen reaction, see Claisen reaction
Models, molecular 51–3
Module
in non-ribosomal peptide biosynthesis 535
in penicillin biosynthesis 538
Molecular models 51–3
ball-and-stick 52
framework 52
space-filling 52
Molecular orbitals 24–35
acetylene 31
ammonia 34
antibonding 24
benzene, antibonding 42
bonding 42
bonding 24
1,3-butadiene, antibonding 38
bonding 38
ethane 28
ethylene 29
Frost circles 43
hydrogen molecule, antibonding 24
bonding 24
methane 27
1,3-pentadiene 37
1,4-pentadiene 37
σ bond 25
π bond 25
in ethylene 29
in acetylene 31
water 34
Molecular rearrangement, see rearrangement
reactions
Molecular representations 1–3
Molecularity, definition 173
Mono-oxygenase, cytochrome
P-450-dependent, see cytochrome P-450
Monosaccharides 463–73
definition 463
Monoterpenes, interconversion through
enolization 353
Morphine
biosynthesis via phenolic oxidative
coupling 343
functional groups, 4
O-glucuronides 489
ionization 163
isoelectric point 163
receptors 514
selective alkylation 186
shape 515
structure 62
Morpholine
conformation 72
structure 404
MRSA (methicillin-resistant Staphylococcus
aureus) 266
Mucopolysaccharide, definition 496
Muscarine, structure 413
Muscarinic acetylcholine receptors 413
Mutarotation, glucose 226
Mycaminose, in spiramycin 494
Mycarose, in spiramycin 494
Mycophenolic acid, structure 385
Mycosamine, in amphotericin 256
NAD + (nicotinamide adenine dinucleotide)
enantiotopic faces 98
as oxidizing agent 237
as pyridinium salt 413, 415
reduction 415
structure 413
NAD
+ and NADP
+
in biological oxidations 576
as nucleotides 560
NADH (reduced nicotinamide adenine
dinucleotide)
as reducing agent 237
from reduction of NAD + 415
in reduction of pyruvic acid 97
prochiral centre 98
NADH and NADPH
in biological reductions 576
as nucleotides 560
NADP
+ (nicotinamide adenine dinucleotide
phosphate)
as pyridinium salt 413
reduction 415
structure 413
NADPH (reduced nicotinamide adenine
dinucleotide phosphate)
as reducing agent 237
Nalbuphine, structure 62
Nalidixic acid, structure 442
Naltrexone, structure 62
Naphthalene
aromaticity 44
electrophilic aromatic substitution 316
Naratriptan, structure 447
NBS, see N-Bromosuccinimide
Neoisomenthol, conformational isomers 70
Neostigmine, as acetylcholinesterase inhibitor
279
Neryl diphosphate 302
allylic cation 197