Subject Index 285
– of hydrogen 234
–, 3-, of a metallic fragment 42
– 1,5- 129
morpholinium salt 170
multistep mechanisms 139
N
N 2 extrusion 202
NaBD 4 39, 44
NaBH 4 43, 45
– reduction 39
naphthamide 183f, 186
negative slope 261
neighboring group 57, 163f, 234
–, amino 156
– mechanism 35ff
– participation 33, 57, 59, 163, 191,
231
–, mechanism 164
– of the ester group 166
– -assisted opening 165
nitro compound 150
nitroalkene 145f, 148
nitroarene 237
nitrobenzene, p-deuterated 238
nitrogen extrusion 143
nitrogen KIE 170
–, heavy atom 173
nitrogen-centered radical 265
nitronate 145ff
– as 1,3-dipole 147
nitrones in the [3+2] cycloaddition
reactions 105
nitrophenol, pK a 157
a
nitrophenol, 4- 113, 118
nitrophenyl N-benzylsulfamate, 4N N
(NPBS) 113, 118
nitropropene, trans-1- 101f
NMM 131
NMR spectroscopy 34, 165, 190
–,
13 C 15, 17, 164f
nonclassical cation 57ff, 269, 272f
nonclassical deltacyclyl cation
intermediate 273
nonclassical intermediate 60, 272
non-coordinating solvent 24
nonlinear dependence 238
non-nucleophilic medium 59
norbornane 269
norbornenes 56, 60
norbornenyl, 7- 61
norbornyl triflates, 2- 55f, 60
nortricyclane 269
nucleofugacity 81, 83, 256
nucleofugal 108
nucleophile 13, 22f, 34, 40, 52, 59, 60,
65, 74f, 93, 127, 181, 191, 205, 221,
235, 238, 241, 257, 272
– and base catalysis mechanisms 67
–, catalysis 63ff, 74, 76, 131, 156,
177ff, 213ff
–, mechanism 181, 215
–, weak 36
nucleophilic 191
– addition 15, 49, 52, 125, 161, 206,
208, 239, 242, 254
– mechanism 48, 50
– to carbonyl groups 22
– and non-nucleophilic media 180
– aromatic substitution 217
– of hydrogen 237
– attack 8ff, 16, 34ff, 48, 75, 94, 135,
144, 164, 170, 178, 181, 191, 205,
209, 214f, 218, 221, 234, 240, 253,
257, 272, 275
– of water 155
– to a C=O group 15
– to an oxirane ring 75
– catalyst 134
– center 9, 237
– counterion 179
– solvent, carbocation rearrangement
59
– solvent participation 90
– substitution 35, 59, 232
– by the solvent 232
–, vicarious 237
– of hydrogen 240
– vinylic substitutions 253, 258
nucleophilicity 173, 196, 213
O
OH
– catalysis 153
–
olefins, trans- 190
optical activity 270
–, loss 271ff
optical rotation 226
ordered transition state 228
organoaluminium reagents 33
organotelluride 189, 191
–, electron-rich 192
orthoester 163ff
– of hydrogen 234
–, 3-, of a metallic fragment 42
– 1,5- 129
morpholinium salt 170
multistep mechanisms 139
N
N 2 extrusion 202
NaBD 4 39, 44
NaBH 4 43, 45
– reduction 39
naphthamide 183f, 186
negative slope 261
neighboring group 57, 163f, 234
–, amino 156
– mechanism 35ff
– participation 33, 57, 59, 163, 191,
231
–, mechanism 164
– of the ester group 166
– -assisted opening 165
nitro compound 150
nitroalkene 145f, 148
nitroarene 237
nitrobenzene, p-deuterated 238
nitrogen extrusion 143
nitrogen KIE 170
–, heavy atom 173
nitrogen-centered radical 265
nitronate 145ff
– as 1,3-dipole 147
nitrones in the [3+2] cycloaddition
reactions 105
nitrophenol, pK a 157
a
nitrophenol, 4- 113, 118
nitrophenyl N-benzylsulfamate, 4N N
(NPBS) 113, 118
nitropropene, trans-1- 101f
NMM 131
NMR spectroscopy 34, 165, 190
–,
13 C 15, 17, 164f
nonclassical cation 57ff, 269, 272f
nonclassical deltacyclyl cation
intermediate 273
nonclassical intermediate 60, 272
non-coordinating solvent 24
nonlinear dependence 238
non-nucleophilic medium 59
norbornane 269
norbornenes 56, 60
norbornenyl, 7- 61
norbornyl triflates, 2- 55f, 60
nortricyclane 269
nucleofugacity 81, 83, 256
nucleofugal 108
nucleophile 13, 22f, 34, 40, 52, 59, 60,
65, 74f, 93, 127, 181, 191, 205, 221,
235, 238, 241, 257, 272
– and base catalysis mechanisms 67
–, catalysis 63ff, 74, 76, 131, 156,
177ff, 213ff
–, mechanism 181, 215
–, weak 36
nucleophilic 191
– addition 15, 49, 52, 125, 161, 206,
208, 239, 242, 254
– mechanism 48, 50
– to carbonyl groups 22
– and non-nucleophilic media 180
– aromatic substitution 217
– of hydrogen 237
– attack 8ff, 16, 34ff, 48, 75, 94, 135,
144, 164, 170, 178, 181, 191, 205,
209, 214f, 218, 221, 234, 240, 253,
257, 272, 275
– of water 155
– to a C=O group 15
– to an oxirane ring 75
– catalyst 134
– center 9, 237
– counterion 179
– solvent, carbocation rearrangement
59
– solvent participation 90
– substitution 35, 59, 232
– by the solvent 232
–, vicarious 237
– of hydrogen 240
– vinylic substitutions 253, 258
nucleophilicity 173, 196, 213
O
OH
– catalysis 153
–
olefins, trans- 190
optical activity 270
–, loss 271ff
optical rotation 226
ordered transition state 228
organoaluminium reagents 33
organotelluride 189, 191
–, electron-rich 192
orthoester 163ff