Page 1331 - Advanced Organic Chemistry Part B - Reactions & Synthesis

1308 Enantioselective catalysts for tin
aldol reaction, 125–133 aldol reactions of, 73–78
Index dihydroxylation of alkenes, 1074–1081 titanium
1,3-dipolar cycloaddition, 536–538 aldol reactions of, 73–78
epoxidation, 1081–1091, 1102–1103 preparation of, 74–75
homogeneous hydrogenation, 377–387 of , -unsaturated, 12
Mukaiyama aldol reaction, 125–133 x-ray crystal structures of
Ene reaction, 869 zirconium
of benzyne, 1041 aldol reactions of, 73–78
Enolate equivalents Enol ethers
in aldol reaction as enolate equivalents, 82–83
in conjugate addition reactions, 190–192 -lithio, as acyl anion equivalents, 1167
Enolates oxidation by singlet oxygen, 1123
acylation of, 150–157 preparation from
examples, 151–152, 156 esters by lombardo’s reagent, 661
aldol reactions carbonyl compounds by wittig reaction,
boron enolates, 71–73 162–163
chelation effects in, 102–105 Enones, see ketones, , -unstaturated
control of stereoselectivity in, 101–108 Ephedrine
lithium enolates, 67–71 chiral auxiliary in aldol reactions, 116–117
tin enolates, 73–78 Epothilone a, multistep synthesis, 1220–1231
titanium enolates, 73–78 alkyne metathesis in, 1225
zirconium enolates, 73–78 macrocyclization by aldol addition, 1224
alkylation of, 21–31 macrolactonization in, 1221
enantioselective, 41–45 nitrile oxide cycloaddition in, 1128
intramolecular, 36–40 olefin metathesis in, 1222
stereoselectivity, of, 24–29, 31–33 Epoxidation, 1081–1103
torsional effect in, 27–28 alkenes
allylation computational model, 1098
palladium-catalyzed, 712–715 by dioxiranes, 1098–1103
arylation enantioselective by manganese diimines,
by chromium tricarbonyl complexes, 769–770 1088–1089
palladium-catalyzed, 728–730 by hydrogen peroxide, 1097
boron hydroxy directing effect, 1093, 1095, 1099
in aldol reactions, 71–73 by peroxycarboxylic acids, 1091–1096
chiral, 117–119 by peroxyimidic acids, 1095–1096
formation of, 72–73 torsional effect on, 1093
stereochemistry of, 71–73 allylic alcohols, 1082–1088
conjugate addition by, 183–189 computational model, 1083–1088
composition of, table, 7–8, 12 mechanism, 1082–1083
formation of, 2–17 sharpless asymmetric, 1082
bases for, 4–5 stereoselectivity, 1085–1086
chelation, affect of, 11 tartrate ligands for, 1082
enantioselective, using a chiral base, 13–14 Epoxides
from enones by reduction, 16–17 acetoxy, rearrangement to acetoxy ketones,
from silyl enol ethers, 14–15, 138 1112–1113
kinetic versus thermodynamic control, 2–10 reactions
regioselectivity of, 5–9 organocopper compounds, 685–686
stereoselectivity of, 9–12, 69–70 rearrangement to carbonyl compounds,
lactam 1111–1112
stereoselective alkylation, 44–45 catalysts for, 1111–1112
lithium reduction by
in aldol reactions, 67–71 diborane, 1110
as nucleophiles, 1 DiBAlH, 1110
oxidation, 1134, 1138–1142 LiALH 4 , 424, 1109–1110
by oxaziridines, 1141–1142 lithium triethylborohydride, 1110
reactivity ring opening, 1104–1109
effect of polyamines on, 21 base-catalyzed, 1114–1116
solvent effects on, 17–21 Lewis acid catalysts for, 1111