Page 1205 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1192 oxazolidinones peroxycarboxylic acids
boron enolates of, 694–695 epoxidation of alkenes by, 504–506
Index as chiral auxiliaries, 207–208, 694–695 peroxy esters
for Diels-Alder reactions, 866 as radical sources, 977
2-oxo-5-hexenyl radical structural effects on rate of decomposition,
cyclization in comparison with 5–hexenyl 1015–1016
radical, 1010–1012 perturbational molecular orbital theory, 41–50
oximes, 646, 651 phase transfer catalysts
configuration of, 121 effect on nucleophilicity, 363–364
formation of, 651–653 phenalene
catalysis of, 653 anion, 757
pH-rate profiles for, 651–652 cation, 757
stability of, 651 Hückel MO diagram for, 757
oxy-Cope rearrangement, 931–932 phenanthrene, 749
anionic, 932 electrophilic aromatic substitution in, 793
origin of rate acceleration in, 932
phenols
transition structure for, 933
solvent effect on alkylation, 368
oxygen
phenonium ion, 423–425
origin of paramagnetism, 7 structure of, 425
reaction with radicals, 1024–1026 phenyl cation, 436, 817
oxymercuration
phosphines
of alkenes, 515–520
BPE, 192
reagents for, 515
chirality of, 129
relative rate for, 516
chiraphos, 192
stereochemistry of, 517–518
DIPAMP, 192
substituent effects in, 518–520
DuPHOS, 192
ozone
as ligand in enantioselective hydrogenation,
MOs of, 49
190–192
reaction with ethene, 49–50
phosphorescence, 1077
phosphorus-containing groups
PA, see proton affinity
carbanion stabilization by, 599
pantolactone
ylides, 599–600
as chiral auxiliary for Diels-Alder reaction,
photochemical reactions, see also photoexcitation
865–866
adiabatic and diabatic transitions, 1075
partial rate factors
alkene photocycloaddition, 1109–1111
for electrophilic aromatic substitution, 786–787
alkene photoisomerization, 1081–1090
bromination, 802
of 1,3-butadienes, 1096–1097
hydrogen exchange, 804–805
of ethene, 1082–1083
nitration, 798
of stilbene, 1085–1090
table of, 788
of styrene, 1083–1085
Paterno-Buchi reaction, 1132–1134
regiochemistry of, 1132–1133 conical intersection, definition, 1080
Pauli exclusion principle, 7, 35 of cyclic alkenes, 1094–6
in relation to rotational barriers, 78–81 cycloaddition of alkenes
1,3-pentadiene computational modeling of, 1109–1110
photoproducts from, 1101–1102 with aromatic compounds, 1136–1137
1,4-pentadiene of dienes, 1100–1104
1,1,5,5–tetraphenyl, photoproducts from, 1114 computational modeling of, 1137–1145
1,5-diphenyl, photoproducts from, 1114 di- -methane rearrangement, 1112–1116
pentafulvalene, 755–757 conical intersection, computational model,
pentalene, 753 1113–1114
3-pentanone mechanism of, 1112–1115
conformation of, 149 stereochemistry of, 1113
4-pentenyl radical electrocyclic reactions, 1099–1100
cyclization of, 1012 fluorescence, 1077
pericyclic reactions, see concerted pericyclic Frank-Condon principle, 1075
reactions general principles, 1073–1080
peroxides internal conversion, 1076
as radical sources, 976–978 intersystem crossing, 1075