Subject Index 281
dimethyl tetrahydro-2(1H)-pyrimidinone, 1,3- 183
dioxycarbenium ion 165ff
dipolar aprotic solvents 257
dipolarophile 101f, 104f, 110, 145ff
dipole 101f, 110, 147
direct in-plane S N 2 vinylic substitution
235
disrotatory electrocyclic ring closure, 6S
161
–, thermal 187
dissociative mechanism 91
dissociative process 172
DMAP 131
DMC 131–137
DMF 212, 252, 257
DMPU 183f, 188
DMSO 207, 218, 252, 257, 263
– -d 6 260
DNFB 217, 220f
Donor Numbers (DN) 22, 24, 206f
double-isotopic fractionation method
244f, 248, 250
E
E1 mechanism 243, 245
E1cB 113, 115, 243, 245
– deprotonation step 247
– elimination 81, 215
– reaction 244
– mechanism 80f, 113, 115, 247
–, irreversible 82, 113, 116ff, 249
– processes 116
– reaction 80
–, reversible, (E1cB) R 82, 113, 115ff
R
(E1cB-like) E2 mechanism 247
E2 115, 243, 245
– elimination 81, 215
– mechanism 80, 83f, 86, 247
– reaction 80f
– transition state 85
– -like mechanism 240
eclipsed conformation 193f
electrocyclic 4S conrotatory ring
opening 160
electrocyclic reaction 97, 161, 183
electrocyclic ring closures 159, 188
–, dearomatizing disrotatory 183
–, 6S disrotatory 161
–, thermal 187
electrocyclic ring openings 159
electrocyclization 97, 188
–, conrotatory 98
electrofugal 108
– group 108
– TMS 111
electron acceptor 266
– in the SET 263
electron-deficient 119
– aromatic rings 217
– dienophiles 119f, 123
– norbornyl triflates 55
– ortho position 183
electron-donating 264
– ability 227
– and -withdrawing substituents 265
– group 75, 121, 139, 142f, 204, 207,
256, 257
– substituents 75, 141f, 204, 207, 261
–, EDG 199
electronic effects 75, 139, 217, 264f
electronic substituent effects 72
electron-poor dienophiles 122
electron-rich dienophiles 119ff, 197ff
electron-rich diorganotellurides 190
electron-rich olefins 122
electron-rich organotellurides 192
electron-withdrawing 16
– group 18, 55f, 58, 60, 75, 121, 123,
139, 143, 155, 215, 258
– substituent 15, 19, 119, 141, 204,
212, 215
–, p-substituents 76
electrophile 65, 129, 187, 242
–, reactive 36
electrophilic addition 18, 30
electrophilic aldehydes 13
electrophilic quenching 184
electrophilicity 23, 155, 182
element effect 252, 256f
elimination 113, 171, 191, 200, 235
– -addition 251, 253
– mechanism 253
–, anti- 84
– processes 85
–, mechanisms of E- 243
–, rate 83
– reactions 79, 243
– step 173, 255
–,E- 239
–, syn 84, 193f
enamines 145
dimethyl tetrahydro-2(1H)-pyrimidinone, 1,3- 183
dioxycarbenium ion 165ff
dipolar aprotic solvents 257
dipolarophile 101f, 104f, 110, 145ff
dipole 101f, 110, 147
direct in-plane S N 2 vinylic substitution
235
disrotatory electrocyclic ring closure, 6S
161
–, thermal 187
dissociative mechanism 91
dissociative process 172
DMAP 131
DMC 131–137
DMF 212, 252, 257
DMPU 183f, 188
DMSO 207, 218, 252, 257, 263
– -d 6 260
DNFB 217, 220f
Donor Numbers (DN) 22, 24, 206f
double-isotopic fractionation method
244f, 248, 250
E
E1 mechanism 243, 245
E1cB 113, 115, 243, 245
– deprotonation step 247
– elimination 81, 215
– reaction 244
– mechanism 80f, 113, 115, 247
–, irreversible 82, 113, 116ff, 249
– processes 116
– reaction 80
–, reversible, (E1cB) R 82, 113, 115ff
R
(E1cB-like) E2 mechanism 247
E2 115, 243, 245
– elimination 81, 215
– mechanism 80, 83f, 86, 247
– reaction 80f
– transition state 85
– -like mechanism 240
eclipsed conformation 193f
electrocyclic 4S conrotatory ring
opening 160
electrocyclic reaction 97, 161, 183
electrocyclic ring closures 159, 188
–, dearomatizing disrotatory 183
–, 6S disrotatory 161
–, thermal 187
electrocyclic ring openings 159
electrocyclization 97, 188
–, conrotatory 98
electrofugal 108
– group 108
– TMS 111
electron acceptor 266
– in the SET 263
electron-deficient 119
– aromatic rings 217
– dienophiles 119f, 123
– norbornyl triflates 55
– ortho position 183
electron-donating 264
– ability 227
– and -withdrawing substituents 265
– group 75, 121, 139, 142f, 204, 207,
256, 257
– substituents 75, 141f, 204, 207, 261
–, EDG 199
electronic effects 75, 139, 217, 264f
electronic substituent effects 72
electron-poor dienophiles 122
electron-rich dienophiles 119ff, 197ff
electron-rich diorganotellurides 190
electron-rich olefins 122
electron-rich organotellurides 192
electron-withdrawing 16
– group 18, 55f, 58, 60, 75, 121, 123,
139, 143, 155, 215, 258
– substituent 15, 19, 119, 141, 204,
212, 215
–, p-substituents 76
electrophile 65, 129, 187, 242
–, reactive 36
electrophilic addition 18, 30
electrophilic aldehydes 13
electrophilic quenching 184
electrophilicity 23, 155, 182
element effect 252, 256f
elimination 113, 171, 191, 200, 235
– -addition 251, 253
– mechanism 253
–, anti- 84
– processes 85
–, mechanisms of E- 243
–, rate 83
– reactions 79, 243
– step 173, 255
–,E- 239
–, syn 84, 193f
enamines 145