Subject Index
282
enantiomer 273, 275
endo adducts 104
endo approach 104, 110
endo mode 145
endo-2-norbornyl derivatives 57
endo-reaction product 111
energies for rotation 179
energy gap 105
enol ethers 145
enolate 214
enthalpy 227
– of activation 115, 118, 228
entropy 227
– of activation 115, 117, 228
epimer 271
epimerization 184, 187f
episulfonium ions 10, 37
– intermediate 9, 35ff
epoxide ring-opening 34f, 163
epoxides 36
epoxy amine, 2,3- 34, 36
epoxy ester-orthoester rearrangement
166
epoxy sulfides 33
esterification 131
– processes 63
Et 3 N 147, 150
ethoxy-3-phenyl-2-propyne, 1- 45
ethyl vinyl ether 197ff, 201
E T
N 50
excited state 111
exo approach 145, 147
– of the alkene 149
exo direction 272
exo-2-norbornyl derivatives 57
exo-mode 265
extrusion of N 2 140, 143, 200
Eyring equation 227
F
F KIE 218ff, 222, 244f, 248
– values 247
facial selectivity 127
Felkin product 127f, 130
–, anti- 128
Felkin-Anh’s model 22, 24f, 127, 130
–, open 25
first-order rate constant 69
fluorescence spectroscopy 111
fluoro nitrobenzenes 241
fluoro-4-(4’-nitrophenyl)butan-2-one, 4243
FMO 102ff, 104, 110, 120f, 123, 145,
199
– energies 106, 120, 122
– energy levels 146
– theory 98, 105
formate 249
free energy 227
Frontier Molecular Orbital see FMO
G
gas constant 227
general base catalyzed 117
glucopyranosyl cation 94
glycols 69
glycopyranosides 87
glucopyranosyl fluoride, D- 92f
ground state 264
group pK a values 154
a
guanacastepene A 1
H
H 2
18 O 73
H 3 O
+ and OH
– catalysis 71
–
half-life of the reaction 225
Hammett
– analysis 139
– constant ҏ U 69, 72, 75, 79, 83ff, 139
– correlation 72
– study 139, 141f, 144
– equation 142
– plot 141, 261, 264
– U value 70, 75, 79, 85
heavy atom KIE 90, 173
heavy atom effects, (primary) 247
helicenes 225
–, [6] 227, 229
heterodienes 145
HMPA (hexamethylphosphoramide)
188, 252, 257
HOMO 98, 102, 105, 121, 123, 145,
199, 201
– -controlled (normal) Diels-Alder
cycloadditions 124
– diene-LUMO dienophile controlled
19
– energy 105, 123
– -LUMO energy gap 102, 106, 121f
hydroazulenone enolate 4
hydrogen bond 92
282
enantiomer 273, 275
endo adducts 104
endo approach 104, 110
endo mode 145
endo-2-norbornyl derivatives 57
endo-reaction product 111
energies for rotation 179
energy gap 105
enol ethers 145
enolate 214
enthalpy 227
– of activation 115, 118, 228
entropy 227
– of activation 115, 117, 228
epimer 271
epimerization 184, 187f
episulfonium ions 10, 37
– intermediate 9, 35ff
epoxide ring-opening 34f, 163
epoxides 36
epoxy amine, 2,3- 34, 36
epoxy ester-orthoester rearrangement
166
epoxy sulfides 33
esterification 131
– processes 63
Et 3 N 147, 150
ethoxy-3-phenyl-2-propyne, 1- 45
ethyl vinyl ether 197ff, 201
E T
N 50
excited state 111
exo approach 145, 147
– of the alkene 149
exo direction 272
exo-2-norbornyl derivatives 57
exo-mode 265
extrusion of N 2 140, 143, 200
Eyring equation 227
F
F KIE 218ff, 222, 244f, 248
– values 247
facial selectivity 127
Felkin product 127f, 130
–, anti- 128
Felkin-Anh’s model 22, 24f, 127, 130
–, open 25
first-order rate constant 69
fluorescence spectroscopy 111
fluoro nitrobenzenes 241
fluoro-4-(4’-nitrophenyl)butan-2-one, 4243
FMO 102ff, 104, 110, 120f, 123, 145,
199
– energies 106, 120, 122
– energy levels 146
– theory 98, 105
formate 249
free energy 227
Frontier Molecular Orbital see FMO
G
gas constant 227
general base catalyzed 117
glucopyranosyl cation 94
glycols 69
glycopyranosides 87
glucopyranosyl fluoride, D- 92f
ground state 264
group pK a values 154
a
guanacastepene A 1
H
H 2
18 O 73
H 3 O
+ and OH
– catalysis 71
–
half-life of the reaction 225
Hammett
– analysis 139
– constant ҏ U 69, 72, 75, 79, 83ff, 139
– correlation 72
– study 139, 141f, 144
– equation 142
– plot 141, 261, 264
– U value 70, 75, 79, 85
heavy atom KIE 90, 173
heavy atom effects, (primary) 247
helicenes 225
–, [6] 227, 229
heterodienes 145
HMPA (hexamethylphosphoramide)
188, 252, 257
HOMO 98, 102, 105, 121, 123, 145,
199, 201
– -controlled (normal) Diels-Alder
cycloadditions 124
– diene-LUMO dienophile controlled
19
– energy 105, 123
– -LUMO energy gap 102, 106, 121f
hydroazulenone enolate 4
hydrogen bond 92