Subject Index
280
crowded eclipsed conformation 194
crowded transition state 172
cyclic voltammetry 262, 266
cyclic-Cram’s model 23, 130
cyclization 97
–, 5-exo 165
–, 6-endo 165
– rate 265
– step 183
cycloaddition 101ff, 107, 119, 198ff
–, 1,3-dipolar 110, 146
–, [3+2] 101f, 145f
–, 1,3-dipoles 145
–, [3+2] dipolar 51
–, [4+2] 146ff, 200
–, inverse electron demand 145
– adduct 198
–, inverse reactions 120
– process 110
cycloadducts 110
cyclobutenone 159, 161
– ring 160
cyclopentadiene 18
cyclopenten-1-ylpyrrolidine, N- 119
N N
cyclopropanations 140
cyclopropylmethyl 61
D
DABCO 211ff
DBU 79, 83, 86, 131–137
dearomatizing disrotatory electrocyclic
ring closure 183
debromination 189, 191, 193f, 196
decarboxylation 108
– product 110
decenyl(phenyl)iodonium tetrafluoroborates, E-1- 231f
decomposition of D-diazo esters 139
deltacyclane 269
deltacyclyl brosylates, 8- 269, 273
departure of the leaving group 272
deuterated media 260
deuteration experiment 4, 59
deuterium 232f
–, KIE 30, 85, 214, 239, 245, 249
–, inverse secondary 240
– label 56, 204f, 243, 270
– -labeling experiments 58, 185, 263
– scrambling 274
– substitution 244
diastereomer 166, 184
diastereoselective reduction 21
diastereoselectivity 21–26, 127, 150
diazabicyclo[2.2.2]octane, 1,4- 211
diazabicyclo[5.4.0]undec-7-ene, 1,879, 131
diazines 197, 199f
diazocompound 140, 143
–, decomposition 144
diazo esters, D- 139
–, decomposition 139
diazo group 143
diazo phenylacetate 141
dibenzylidene succinates, E,E- 97, 100
dibromide 191
–, erythro- 190
dibromocycloalkanes, trans-1,2- 190,
193
dibromodecane, 1,2- 190, 194
dibromo-1,2-diphenylethane, 1,2- 190
dibromo-2-methyl-1-phenylpropane,
1,2- 190, 194
Diels-Alder
– electron demand 200
– inverse electron demand 119,
121ff, 197, 199
– mechanism 229
–, normal reaction 18, 120ff
– reaction 14, 119ff, 197, 199, 216,
229
–, retro-cycloaddition 199
–, retro-process 200, 202
dienophile 19, 120f, 145, 148, 197, 199,
201f
–, electron-poor 122
–, electron-rich 119ff, 197ff
diethyl fumarate 119, 121
dihydronaphthalene 97f
–, 1,2- 100
–, cis- 97
–, trans- 97, 99
dimethylaminophenyl azadiene, 4-N, N N N- N N
123
dimethylaminopyridine, 4-(N ( ( ,
N N N) N N
(DMAP) 131
–, pK a 170
a
dimethyl aniline, N, N N N-, pK
N N
a 170
a
dimethyl-2-butene, 2,3- 146, 148
dimethyl carbonate 131
dimethyl formamide, N, N N N- N N see DMF
dimethyl sulfate 131
280
crowded eclipsed conformation 194
crowded transition state 172
cyclic voltammetry 262, 266
cyclic-Cram’s model 23, 130
cyclization 97
–, 5-exo 165
–, 6-endo 165
– rate 265
– step 183
cycloaddition 101ff, 107, 119, 198ff
–, 1,3-dipolar 110, 146
–, [3+2] 101f, 145f
–, 1,3-dipoles 145
–, [3+2] dipolar 51
–, [4+2] 146ff, 200
–, inverse electron demand 145
– adduct 198
–, inverse reactions 120
– process 110
cycloadducts 110
cyclobutenone 159, 161
– ring 160
cyclopentadiene 18
cyclopenten-1-ylpyrrolidine, N- 119
N N
cyclopropanations 140
cyclopropylmethyl 61
D
DABCO 211ff
DBU 79, 83, 86, 131–137
dearomatizing disrotatory electrocyclic
ring closure 183
debromination 189, 191, 193f, 196
decarboxylation 108
– product 110
decenyl(phenyl)iodonium tetrafluoroborates, E-1- 231f
decomposition of D-diazo esters 139
deltacyclane 269
deltacyclyl brosylates, 8- 269, 273
departure of the leaving group 272
deuterated media 260
deuteration experiment 4, 59
deuterium 232f
–, KIE 30, 85, 214, 239, 245, 249
–, inverse secondary 240
– label 56, 204f, 243, 270
– -labeling experiments 58, 185, 263
– scrambling 274
– substitution 244
diastereomer 166, 184
diastereoselective reduction 21
diastereoselectivity 21–26, 127, 150
diazabicyclo[2.2.2]octane, 1,4- 211
diazabicyclo[5.4.0]undec-7-ene, 1,879, 131
diazines 197, 199f
diazocompound 140, 143
–, decomposition 144
diazo esters, D- 139
–, decomposition 139
diazo group 143
diazo phenylacetate 141
dibenzylidene succinates, E,E- 97, 100
dibromide 191
–, erythro- 190
dibromocycloalkanes, trans-1,2- 190,
193
dibromodecane, 1,2- 190, 194
dibromo-1,2-diphenylethane, 1,2- 190
dibromo-2-methyl-1-phenylpropane,
1,2- 190, 194
Diels-Alder
– electron demand 200
– inverse electron demand 119,
121ff, 197, 199
– mechanism 229
–, normal reaction 18, 120ff
– reaction 14, 119ff, 197, 199, 216,
229
–, retro-cycloaddition 199
–, retro-process 200, 202
dienophile 19, 120f, 145, 148, 197, 199,
201f
–, electron-poor 122
–, electron-rich 119ff, 197ff
diethyl fumarate 119, 121
dihydronaphthalene 97f
–, 1,2- 100
–, cis- 97
–, trans- 97, 99
dimethylaminophenyl azadiene, 4-N, N N N- N N
123
dimethylaminopyridine, 4-(N ( ( ,
N N N) N N
(DMAP) 131
–, pK a 170
a
dimethyl aniline, N, N N N-, pK
N N
a 170
a
dimethyl-2-butene, 2,3- 146, 148
dimethyl carbonate 131
dimethyl formamide, N, N N N- N N see DMF
dimethyl sulfate 131