Subject Index
286
orthoesterol B 166
overlapping 98, 199, 201
– between lobes 103
– between orbitals 98
– between two atoms 147
oxacarbenium ion 87ff
– intermediate 92
oxazoline N-oxide 101f, 105
N N
oxidant reagent 267
oxidant species 263
oxidation 6
– of an alcohol 4
– potential 262, 266
oxirane 36
oxonium ion 30f
P
parallel reactions 40
PDKIE 81ff, 238, 245, 248f
peptide bond formation 169
pericyclic reaction 100, 187f
periodinane 259
– -mediated cyclizations 263
– of anilides 259
perpendicular nucleophilic attack 251ff
pH dependent 153
phenol 63ff
–, pK a 157
a
– -d 6 67
phenonium ion 234
phenyl 2-aminobenzoate 153
phenylacetylene 201, 231ff, 251ff
phenylnorbornyl, 2- 61
phenylsulfonylbenzaldimine, N- 203
N N
phenylthioamides, N- 262
N N
phenylthioindole, 3- 8f
phenylthioindole, 2,3-bis- 8f
photochemical ring closure 97f
photodecarboxylation 108f
photoinduced single electron transfer
see SET
phthalimide system 111
phthalimidobutyric acid, N- 109
N N
phthaloyl derivatives, N- 111
N N
phthaloyl D-amino acid, N- 107ff
N N
phthaloyl glutamic acid, N- 108
N N
pinacolone enolsilane 125, 128
pK a 68, 115ff, 150, 156
a
– of the amino group 153
– of the base 246
– values 64
planar carbanion 254
Planck constant 227
polar intermediate 215
polarimetry 225
polycyclic amides 183
pre-equilibrium 66, 73, 140, 143, 239
pre-exponential factor 226
principle of maximum overlap 104
protonation-rotation 177ff
–, pathway 181
pseudo second-order constant 221
pseudo-first order rate law 141, 153
pyranosides 91
Q
quenching 184ff
– D 2 O 186
–, electrophilic 184
R
racemization 225ff, 273ff
– of helicenes 229
– process 226f
– rate 227ff
radical 259ff
–, amide 262
– cation 259, 264, 267
– cyclization 264, 266
– reaction 259
–, hydrogen 259
– mechanism 259, 263
– process 262, 265
– quenchers 263
– species 265
– translocation 186
rate constant 220, 238
rate-determining step 66f, 72, 82, 91,
116ff, 139, 157, 173, 205, 216ff, 237,
238, 245, 252, 256, 260, 266
– in the S N Ar reaction 217
rate expression 66, 212
rate law 66f, 220f
–, general 114
rate limiting 87, 92, 140, 217, 239
– nucleophilic addition 221
– step 116
reaction rate 244, 261, 271
reactive conformation 22
reactive short-lived species 239
rearrangement 27, 30ff, 42, 159, 162f,
166, 273
286
orthoesterol B 166
overlapping 98, 199, 201
– between lobes 103
– between orbitals 98
– between two atoms 147
oxacarbenium ion 87ff
– intermediate 92
oxazoline N-oxide 101f, 105
N N
oxidant reagent 267
oxidant species 263
oxidation 6
– of an alcohol 4
– potential 262, 266
oxirane 36
oxonium ion 30f
P
parallel reactions 40
PDKIE 81ff, 238, 245, 248f
peptide bond formation 169
pericyclic reaction 100, 187f
periodinane 259
– -mediated cyclizations 263
– of anilides 259
perpendicular nucleophilic attack 251ff
pH dependent 153
phenol 63ff
–, pK a 157
a
– -d 6 67
phenonium ion 234
phenyl 2-aminobenzoate 153
phenylacetylene 201, 231ff, 251ff
phenylnorbornyl, 2- 61
phenylsulfonylbenzaldimine, N- 203
N N
phenylthioamides, N- 262
N N
phenylthioindole, 3- 8f
phenylthioindole, 2,3-bis- 8f
photochemical ring closure 97f
photodecarboxylation 108f
photoinduced single electron transfer
see SET
phthalimide system 111
phthalimidobutyric acid, N- 109
N N
phthaloyl derivatives, N- 111
N N
phthaloyl D-amino acid, N- 107ff
N N
phthaloyl glutamic acid, N- 108
N N
pinacolone enolsilane 125, 128
pK a 68, 115ff, 150, 156
a
– of the amino group 153
– of the base 246
– values 64
planar carbanion 254
Planck constant 227
polar intermediate 215
polarimetry 225
polycyclic amides 183
pre-equilibrium 66, 73, 140, 143, 239
pre-exponential factor 226
principle of maximum overlap 104
protonation-rotation 177ff
–, pathway 181
pseudo second-order constant 221
pseudo-first order rate law 141, 153
pyranosides 91
Q
quenching 184ff
– D 2 O 186
–, electrophilic 184
R
racemization 225ff, 273ff
– of helicenes 229
– process 226f
– rate 227ff
radical 259ff
–, amide 262
– cation 259, 264, 267
– cyclization 264, 266
– reaction 259
–, hydrogen 259
– mechanism 259, 263
– process 262, 265
– quenchers 263
– species 265
– translocation 186
rate constant 220, 238
rate-determining step 66f, 72, 82, 91,
116ff, 139, 157, 173, 205, 216ff, 237,
238, 245, 252, 256, 260, 266
– in the S N Ar reaction 217
rate expression 66, 212
rate law 66f, 220f
–, general 114
rate limiting 87, 92, 140, 217, 239
– nucleophilic addition 221
– step 116
reaction rate 244, 261, 271
reactive conformation 22
reactive short-lived species 239
rearrangement 27, 30ff, 42, 159, 162f,
166, 273