Subject Index
284
–, F 218ff, 222, 244f, 248
–, heavy atom 90
–, inverse values 89
–, inverse ring
18
O 89
– values 247
–, nitrogen 170
–, heavy atom 173
–, normal values 89
–, primary deuterium (PDKIE) 81ff,
238, 245, 248f
–, primary 83, 239, 249
– secondary deuterium (SDKIE) 91,
238, 244ff
–, E- 91
–, secondary F- 244, 247
–, secondary (SKIE) 91, 239f
–, D- and E- 91
–, values 238, 240
kinetic analysis 220
kinetic control 186
kinetic data 67, 238, 266
kinetic isotope data 88, 90, 245
kinetic isotope effect see KIE
kinetic law 213f, 221
kinetic study 65, 204
Knoevenagel cyclization 1–6
–, mechanism 4
L
labeled 179, 274
– benzoic acid 134
– compound 272
–,
18 O- 164
– substrate 214
labeling experiment 108, 232f, 272
–, crossover- 28
lactams,J- 259
lactones 47
laser flash photolysis 111
leaving group 63, 81ff, 113, 116, 156,
243, 245, 254
–, ability 156, 236, 256
–, basicity 81
–, F, KIEs 244
–, KIEs 247
–
18 O 88f
–, KIE 90
–
18 OMe, KIE 89
–, pK a 84
a
Lewis acid 13–16, 19–27, 36, 51, 125ff
– CeCl 3 24
– -catalyzed Diels-Alder reactions 19
– mediated nucleophilic addition to a
carbonyl group 16
lifetime, estimated 93f
lifetime of a carbocation 60, 77
lignans 97
linear dependence 212
lithiation 185
– of N-benzoyl oxazolidine 184f
lithio-3-phenyl-1-propyne, 1- 159f
lithium triethylborohydride 21
long-lived intermediates 67
LUMO 19, 98, 103, 105, 121, 123, 145,
198ff
– energy 19
– -controlled (inverse) Diels-Alder
cycloadditions 124
M
magnitude of U obs 144
Me 2 AlCl 125ff
Me 3 Al 34ff
mechanism, polar 47
Meisenheimer intermediate 217ff, 221
methanediol 89
methanesulfenyl chloride 8f
methanol 212, 232
methanolysis of (+)-styrene oxide, acid
70
p-methoxy-E-bromostyrenes, Z-/ Z Z E
/ / - 252
methyl acrylate 107, 109, 111
methylating agent 131f, 137
methylating reagent, N- 134
methyl butenoate, trans-2- 102
methyl chloroformate 133
methyl hydroxylamine, N- 47ff
methyl D-thioxylopyranosides 88
methyl D-xylopyranosides 88
methyl hydroxylamine, O- 47, 49, 52
methyl iodide 11, 131
methyl morpholine, N- 131, 169, 171,
175
–, KIE 173
–, pK a 170
a
methyl propenoate 145
methyl trifluoromethanesulfonate 11
methyl xylopyranosides 89
Michael-type addition 160
Michael-type reactivity 48
migration
–, H-shift 59
284
–, F 218ff, 222, 244f, 248
–, heavy atom 90
–, inverse values 89
–, inverse ring
18
O 89
– values 247
–, nitrogen 170
–, heavy atom 173
–, normal values 89
–, primary deuterium (PDKIE) 81ff,
238, 245, 248f
–, primary 83, 239, 249
– secondary deuterium (SDKIE) 91,
238, 244ff
–, E- 91
–, secondary F- 244, 247
–, secondary (SKIE) 91, 239f
–, D- and E- 91
–, values 238, 240
kinetic analysis 220
kinetic control 186
kinetic data 67, 238, 266
kinetic isotope data 88, 90, 245
kinetic isotope effect see KIE
kinetic law 213f, 221
kinetic study 65, 204
Knoevenagel cyclization 1–6
–, mechanism 4
L
labeled 179, 274
– benzoic acid 134
– compound 272
–,
18 O- 164
– substrate 214
labeling experiment 108, 232f, 272
–, crossover- 28
lactams,J- 259
lactones 47
laser flash photolysis 111
leaving group 63, 81ff, 113, 116, 156,
243, 245, 254
–, ability 156, 236, 256
–, basicity 81
–, F, KIEs 244
–, KIEs 247
–
18 O 88f
–, KIE 90
–
18 OMe, KIE 89
–, pK a 84
a
Lewis acid 13–16, 19–27, 36, 51, 125ff
– CeCl 3 24
– -catalyzed Diels-Alder reactions 19
– mediated nucleophilic addition to a
carbonyl group 16
lifetime, estimated 93f
lifetime of a carbocation 60, 77
lignans 97
linear dependence 212
lithiation 185
– of N-benzoyl oxazolidine 184f
lithio-3-phenyl-1-propyne, 1- 159f
lithium triethylborohydride 21
long-lived intermediates 67
LUMO 19, 98, 103, 105, 121, 123, 145,
198ff
– energy 19
– -controlled (inverse) Diels-Alder
cycloadditions 124
M
magnitude of U obs 144
Me 2 AlCl 125ff
Me 3 Al 34ff
mechanism, polar 47
Meisenheimer intermediate 217ff, 221
methanediol 89
methanesulfenyl chloride 8f
methanol 212, 232
methanolysis of (+)-styrene oxide, acid
70
p-methoxy-E-bromostyrenes, Z-/ Z Z E
/ / - 252
methyl acrylate 107, 109, 111
methylating agent 131f, 137
methylating reagent, N- 134
methyl butenoate, trans-2- 102
methyl chloroformate 133
methyl hydroxylamine, N- 47ff
methyl D-thioxylopyranosides 88
methyl D-xylopyranosides 88
methyl hydroxylamine, O- 47, 49, 52
methyl iodide 11, 131
methyl morpholine, N- 131, 169, 171,
175
–, KIE 173
–, pK a 170
a
methyl propenoate 145
methyl trifluoromethanesulfonate 11
methyl xylopyranosides 89
Michael-type addition 160
Michael-type reactivity 48
migration
–, H-shift 59