Subject Index
288
–, deuterium KIES 92
–, dipolar aprotic 257
– effects 37, 203
–, hydrogen-donating 263
– -isotope effect 156
– (kD 3 O
+
/kH 3 O
+ ) 88f
–, KIEs 92
– molecules 73
–, non-coordinating 24
–, nucleophilicity 59
–, polar 192, 215
–, polarity 50f, 196, 207
– -separated fragments 28, 31
solvolysis 55f, 60, 232, 234, 269, 271,
273, 275f
–, acid 73
–, direct 73
– in acetic acid 231
– in AcOH or MeOH 235
–, mechanism 271
– of 8-deltacyclyl brosylates 269
– of p-substituted styrene oxides 76
– of vinyl iodonium salts 231
–, process 57f
–, rate 270
–, reactions 273
specific acid catalysis 72f, 76, 87, 92
– protonation 87
specific rotation 225
steady-state approximation 220, 222,
238, 239
stepwise elimination 115
stepwise mechanism 111, 144, 169,
212, 238, 257
–, acid-promoted 99
stepwise process 27, 30f, 60, 81, 187
stereochemical control 24
stereoselective 23, 104f, 125f, 128, 130,
183, 192, 195f, 204, 208, 252
– cyclization reaction 183
– debromination 189
– reaction 203, 206
– synthesis of 2-acylaziridines 203
–, total 125, 187
stereospecific 33, 36, 252
– reaction 253
– ring-opening 37
– substitution reactions 33
steric effects 217
steric factors 194
steric hindrance 170ff
steric interactions 193f
steric strain 84
sterically crowded 174
– transition state 172f
stilbene, trans- 195f
styrene oxide 69f, 74f, 77
–, (+)- 73
–, p-substituted 69
styryl(phenyl)iodonium tetrafluoroborate, E- 231ff
substituent constant V
+ 141, 144
substitution 235
– of E-halostyrenes 251
succinate, irradiation of 97
sulfamides 113, 116
sulfenyl chloride 7ff
sulfenylation 7f
– of indoles 7
– -rearrangement mechanism 9
sulfide, bis- 8
sulfonyl chloride 10
sulfonyl imines 207
sulfonyl imines, N- 204
sulfonyl oxygen 208
symmetric, C 2 - 229
symmetry, C s - 228
syn elimination 84, 193f
syn-D-methyl-E-alkoxy aldehydes 125
T
t 1/2 225ff
tandem cycloadditions 145
tandem intermolecular [4+2]/ intramolecular [3+2] cycloaddition 148
TEA 160
telluride 189ff
– as a scavenger 196
telluronium salt 191
temperature, absolute 227
tertiary amine 169ff, 212f
tertiary carbanion 237, 242
tetrafluoroboric acid 178
tetrahedral intermediate 178, 180
tetrahydropyran derivatives 27, 32
tetrahydropyranyl ethers 27
tetrahydropyridine 119
tetrazine 197ff
TFA 56, 59
TFE 235
THF 263
– :DMSO 208
288
–, deuterium KIES 92
–, dipolar aprotic 257
– effects 37, 203
–, hydrogen-donating 263
– -isotope effect 156
– (kD 3 O
+
/kH 3 O
+ ) 88f
–, KIEs 92
– molecules 73
–, non-coordinating 24
–, nucleophilicity 59
–, polar 192, 215
–, polarity 50f, 196, 207
– -separated fragments 28, 31
solvolysis 55f, 60, 232, 234, 269, 271,
273, 275f
–, acid 73
–, direct 73
– in acetic acid 231
– in AcOH or MeOH 235
–, mechanism 271
– of 8-deltacyclyl brosylates 269
– of p-substituted styrene oxides 76
– of vinyl iodonium salts 231
–, process 57f
–, rate 270
–, reactions 273
specific acid catalysis 72f, 76, 87, 92
– protonation 87
specific rotation 225
steady-state approximation 220, 222,
238, 239
stepwise elimination 115
stepwise mechanism 111, 144, 169,
212, 238, 257
–, acid-promoted 99
stepwise process 27, 30f, 60, 81, 187
stereochemical control 24
stereoselective 23, 104f, 125f, 128, 130,
183, 192, 195f, 204, 208, 252
– cyclization reaction 183
– debromination 189
– reaction 203, 206
– synthesis of 2-acylaziridines 203
–, total 125, 187
stereospecific 33, 36, 252
– reaction 253
– ring-opening 37
– substitution reactions 33
steric effects 217
steric factors 194
steric hindrance 170ff
steric interactions 193f
steric strain 84
sterically crowded 174
– transition state 172f
stilbene, trans- 195f
styrene oxide 69f, 74f, 77
–, (+)- 73
–, p-substituted 69
styryl(phenyl)iodonium tetrafluoroborate, E- 231ff
substituent constant V
+ 141, 144
substitution 235
– of E-halostyrenes 251
succinate, irradiation of 97
sulfamides 113, 116
sulfenyl chloride 7ff
sulfenylation 7f
– of indoles 7
– -rearrangement mechanism 9
sulfide, bis- 8
sulfonyl chloride 10
sulfonyl imines 207
sulfonyl imines, N- 204
sulfonyl oxygen 208
symmetric, C 2 - 229
symmetry, C s - 228
syn elimination 84, 193f
syn-D-methyl-E-alkoxy aldehydes 125
T
t 1/2 225ff
tandem cycloadditions 145
tandem intermolecular [4+2]/ intramolecular [3+2] cycloaddition 148
TEA 160
telluride 189ff
– as a scavenger 196
telluronium salt 191
temperature, absolute 227
tertiary amine 169ff, 212f
tertiary carbanion 237, 242
tetrafluoroboric acid 178
tetrahedral intermediate 178, 180
tetrahydropyran derivatives 27, 32
tetrahydropyranyl ethers 27
tetrahydropyridine 119
tetrazine 197ff
TFA 56, 59
TFE 235
THF 263
– :DMSO 208