Subject Index 283
hydrogen radical 259
hydrogen-donating solvent 263
hydrolysis 69, 74f, 87ff, 94, 153ff, 163
– for orthoester 165
– in H 2
18 O 70
– mechanism 87
– of (+)-styrene oxide 70
– of an ester 157
– of methyl 5-thioxylopyranosides 92
– of phenyl 2-aminobenzoate 155
– of phenyl 4-aminobenzoate 155
– of styrene oxides 71
– of thioxylopyranosides 90
– of xylopyranoses 92
– of xylopyranosides 90
– rate 155
hydroximates 178ff
hydroximoyl chloride 178f, 181f
1-hydroxy-1,2-benziodoxol-3(1H)-one1-oxide, IBX 259
hydroxylamine 48, 51f
– derivatives 47f
hyperconjugation 18, 91, 254f
hyperconjugative stabilizing effect 254
I
IBX 259, 263, 266f
– -mediated 264
imidazol 249
imines 177, 203, 205f
iminium ion, rotation energy barrier 181
indole 7
indolyl bis-sulfides, 2,3- 7
initial induction period 175
in-plane concerted substitution mechanism 252
in-plane S N 2 vinylic substitution 233f
in-plane S N 2-type substitution 251
insertion, Si–H- 141
intermediate V-adduct 239
intermolecular 30
– mechanism 32
intramolecular 30
– base catalysis 156
– conjugate addition 183
– coordination 207
– [3+2] cycloaddition 149f
– [4+2] cycloaddition 202
– general base catalysis 153
– nucleophilic attack 206
– proton transfer 110, 186
– rearrangement 30
– ring opening of the epoxide 35
– S N 2 reaction 209
– transesterification 49, 51
inverse cycloaddition reactions 120
inverse electron demand Diels-Alder
reaction 119, 121ff, 197, 199
inverse KIE values 89
inverse ring
18 O KIE 89
inverse secondary deuterium isotope
effect 240
inversion of the configuration 192, 232
– at the anomeric carbon 93
inversion of the stereochemistry 233,
253
inversion products 94
inverted solvolysis products 233
iodobenzene 205, 231, 233f
iodonium 234
– ylide 203, 205, 209
ion pair 31
isodeltacyclyl brosylates 271
isolobal analogy principle 40
isomer, erythro- 190
isomerization 178ff, 273ff
–, alkyne-allene base-catalyzed 161
–, E/ E E Z
/ / 177, 182
Z
– of imines 177
– rate 179
isopolar 50
isotope effect 67, 79
isotope labeling experiments 30, 39, 47,
73, 131, 163, 229, 260, 263
isoxazolidinone 47ff
isoxazolines 147ff
–, bicyclic 149
K
K
18 OH/H 2
18 O 74f
ketene formation 64
ketene intermediates 63
keto ester,E- 1, 3, 21
keto group 4
ketones 13
k H /k D 79, 81, 84f
KIE 67f, 87ff, 169, 212, 214, 217, 238,
243, 248
–, D- 91
–,
13 C 90f
–, chlorine 170, 173
–, D 30, 85, 214, 239, 245, 249
hydrogen radical 259
hydrogen-donating solvent 263
hydrolysis 69, 74f, 87ff, 94, 153ff, 163
– for orthoester 165
– in H 2
18 O 70
– mechanism 87
– of (+)-styrene oxide 70
– of an ester 157
– of methyl 5-thioxylopyranosides 92
– of phenyl 2-aminobenzoate 155
– of phenyl 4-aminobenzoate 155
– of styrene oxides 71
– of thioxylopyranosides 90
– of xylopyranoses 92
– of xylopyranosides 90
– rate 155
hydroximates 178ff
hydroximoyl chloride 178f, 181f
1-hydroxy-1,2-benziodoxol-3(1H)-one1-oxide, IBX 259
hydroxylamine 48, 51f
– derivatives 47f
hyperconjugation 18, 91, 254f
hyperconjugative stabilizing effect 254
I
IBX 259, 263, 266f
– -mediated 264
imidazol 249
imines 177, 203, 205f
iminium ion, rotation energy barrier 181
indole 7
indolyl bis-sulfides, 2,3- 7
initial induction period 175
in-plane concerted substitution mechanism 252
in-plane S N 2 vinylic substitution 233f
in-plane S N 2-type substitution 251
insertion, Si–H- 141
intermediate V-adduct 239
intermolecular 30
– mechanism 32
intramolecular 30
– base catalysis 156
– conjugate addition 183
– coordination 207
– [3+2] cycloaddition 149f
– [4+2] cycloaddition 202
– general base catalysis 153
– nucleophilic attack 206
– proton transfer 110, 186
– rearrangement 30
– ring opening of the epoxide 35
– S N 2 reaction 209
– transesterification 49, 51
inverse cycloaddition reactions 120
inverse electron demand Diels-Alder
reaction 119, 121ff, 197, 199
inverse KIE values 89
inverse ring
18 O KIE 89
inverse secondary deuterium isotope
effect 240
inversion of the configuration 192, 232
– at the anomeric carbon 93
inversion of the stereochemistry 233,
253
inversion products 94
inverted solvolysis products 233
iodobenzene 205, 231, 233f
iodonium 234
– ylide 203, 205, 209
ion pair 31
isodeltacyclyl brosylates 271
isolobal analogy principle 40
isomer, erythro- 190
isomerization 178ff, 273ff
–, alkyne-allene base-catalyzed 161
–, E/ E E Z
/ / 177, 182
Z
– of imines 177
– rate 179
isopolar 50
isotope effect 67, 79
isotope labeling experiments 30, 39, 47,
73, 131, 163, 229, 260, 263
isoxazolidinone 47ff
isoxazolines 147ff
–, bicyclic 149
K
K
18 OH/H 2
18 O 74f
ketene formation 64
ketene intermediates 63
keto ester,E- 1, 3, 21
keto group 4
ketones 13
k H /k D 79, 81, 84f
KIE 67f, 87ff, 169, 212, 214, 217, 238,
243, 248
–, D- 91
–,
13 C 90f
–, chlorine 170, 173
–, D 30, 85, 214, 239, 245, 249