Subject Index 289
– -d 8 260
thiacarbenium ion 88, 90ff
– intermediate 92
thioglycopyranosides, 5- 87
thioglucopyranosyl cation, 5- 94
thioglucopyranosyl fluoride, 5- 92, 94
thioxylopyranosides 90
third-order kinetic law 66
third-order overall rate 64
threo-dibromides 190
through conjugation 72, 264
TiCl 4 21
tin alkoxide 30
tin hydride 262
TMSCl 147, 150
tolualdehyde, p- 14
toluidine p- 218, 221
toluidines, o- and p- 217
toluidine, o- 218, 220f
trajectory 22
transesterification 4, 49ff
transition state 75, 79– 86, 91, 98, 144,
150, 172ff, 207f, 215, 219, 229, 233,
245ff, 252, 264
–, C s 228
–, conrotatory 98
–, endo- 104
–, exo- 104
– for the addition of a nucleophile to
a carbonyl group 22
– geometry 92
–, polar 50
–, symmetrical 84
–, theory 227f
trapping agent 76f, 110
trapping experiment 77
triazine
– carbocation 170
– cation 172
–, 2-, chloro-4,6-dimethoxy-1,3,5169
–, 2-, chloro-1,3,5- 169, 174
– ring 172
– super active esters 169
triazinyl ammonium 169, 172
– salt 169, 174
tributyl amine 131, 174
–, pK a 170
a
triethylamine 160
–, pK a 170
a
triethylsilane 141
triflates 59
–, endo- 56, 59
–, exo- 56, 59
triflic acid 97, 99, 178
trifluoroacetic acid 56
trifluoroacetophenone 15
trifluoroethanol, pK a 157
a
trifluoroethanol, 2,2,2- (TFE) 232
(2,2,2-trifluoroethoxy)styrene, E- 232
trifluoromethanesulfonic acid 97, 178
trifluoromethylbenzaldehyde, p- 14
trimethoxybenzene, 1,2,3- 100
trimethylamine 170, 174
–, pK a 170
a
trimethyl oxazoline N-oxide, 2,4,4- 105
N N
trimethyl-1-phenyl-1-butanone, 2,3,325
trimethylpyrrolidine N-oxide, , 2,2,5105
trimethylsilyl chloride (TMSCl) 147
(trimethylsilyl)methylphthalimide, N- N N
111
trimethylsilyl trifluoromethanesulfonate
(TMSOTf) 34
U
unimolecular rate-determining step 117
unsaturated systems, D,E- 52
–, aldehydes 19
–, alkoxychromium(0) carbenes 39f,
43
–, esters 47f
–, ketones 14, 19
–, nitroalkenes 101
unsymmetrical E2 process 247
upfield shifts 164
UV absorptions 64
UV-vis experiments 67f
V, W
vicarious nucleophilic substitution
(VNS) 237ff
–, mechanism 242
– of hydrogen 240
–, products 241
–, reaction 237
vicinal dibromides 189f
vinyl ether 39f
vinyl iodonium salt 231ff
–, D-deuterated 204
– -d 8 260
thiacarbenium ion 88, 90ff
– intermediate 92
thioglycopyranosides, 5- 87
thioglucopyranosyl cation, 5- 94
thioglucopyranosyl fluoride, 5- 92, 94
thioxylopyranosides 90
third-order kinetic law 66
third-order overall rate 64
threo-dibromides 190
through conjugation 72, 264
TiCl 4 21
tin alkoxide 30
tin hydride 262
TMSCl 147, 150
tolualdehyde, p- 14
toluidine p- 218, 221
toluidines, o- and p- 217
toluidine, o- 218, 220f
trajectory 22
transesterification 4, 49ff
transition state 75, 79– 86, 91, 98, 144,
150, 172ff, 207f, 215, 219, 229, 233,
245ff, 252, 264
–, C s 228
–, conrotatory 98
–, endo- 104
–, exo- 104
– for the addition of a nucleophile to
a carbonyl group 22
– geometry 92
–, polar 50
–, symmetrical 84
–, theory 227f
trapping agent 76f, 110
trapping experiment 77
triazine
– carbocation 170
– cation 172
–, 2-, chloro-4,6-dimethoxy-1,3,5169
–, 2-, chloro-1,3,5- 169, 174
– ring 172
– super active esters 169
triazinyl ammonium 169, 172
– salt 169, 174
tributyl amine 131, 174
–, pK a 170
a
triethylamine 160
–, pK a 170
a
triethylsilane 141
triflates 59
–, endo- 56, 59
–, exo- 56, 59
triflic acid 97, 99, 178
trifluoroacetic acid 56
trifluoroacetophenone 15
trifluoroethanol, pK a 157
a
trifluoroethanol, 2,2,2- (TFE) 232
(2,2,2-trifluoroethoxy)styrene, E- 232
trifluoromethanesulfonic acid 97, 178
trifluoromethylbenzaldehyde, p- 14
trimethoxybenzene, 1,2,3- 100
trimethylamine 170, 174
–, pK a 170
a
trimethyl oxazoline N-oxide, 2,4,4- 105
N N
trimethyl-1-phenyl-1-butanone, 2,3,325
trimethylpyrrolidine N-oxide, , 2,2,5105
trimethylsilyl chloride (TMSCl) 147
(trimethylsilyl)methylphthalimide, N- N N
111
trimethylsilyl trifluoromethanesulfonate
(TMSOTf) 34
U
unimolecular rate-determining step 117
unsaturated systems, D,E- 52
–, aldehydes 19
–, alkoxychromium(0) carbenes 39f,
43
–, esters 47f
–, ketones 14, 19
–, nitroalkenes 101
unsymmetrical E2 process 247
upfield shifts 164
UV absorptions 64
UV-vis experiments 67f
V, W
vicarious nucleophilic substitution
(VNS) 237ff
–, mechanism 242
– of hydrogen 240
–, products 241
–, reaction 237
vicinal dibromides 189f
vinyl ether 39f
vinyl iodonium salt 231ff
–, D-deuterated 204