Page 1185 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1172 adamantane (cont.) stereospecificity of, 183–185, 487–489
halides, substitution reactions, 1052 chlorination, 487–488
Index structure of, 166 rearrangement during, 494
adamantanone configuration of, 113
polar effects in reduction of, 238–239 conformation of, 145–148
AIBN, see azoisobutyronitrile bisected, definition, 145
AIM, see atoms in molecules approach eclipsed, definition, 145
Albery-More O’Ferrall-Jencks diagram, see cyclic, photoreactions of, 1094
potential energy diagram, two-dimensional cycloaddition reactions with enones, 1125–1126
alcohol dehydrogenase dihydroxylation of, 186
enantiospecificity of, 135 computational model for, 202–203
alcohols enantioselective, 200–203
acetal formation, 640 electrophilic addition reactions of, 473–476
acidity of, 104–105 comparison of, 531–536
acylation of, 664–667 mechanisms for, 474–478
acylium ions as intermediates, 664–665 enthalpy of formation, 256–257
carbodiimides in, 667 epoxidation, 186–187, 503–511
allylic by dimethyldioxirane, 507–510
enantioselective epoxidation of, 196–199 fluorination
dehydration of, 474, 563–564 reagents for, 496
esterification of, 664–668 halogenation, 485–497
nucleophilic catalysis in, 665 relative rate in, table, 487
synthesis using organoboranes, 527–528 stereochemistry of, 487–488
aldehydes, see also carbonyl compounds hydration of, 474, 482–484
addition reactions of, 629–632 relative rates of, table, 484
conformation of, 148 hydroboration of, 521–526
cyanohydrins from, 635 electrophilic character of, 522
imine formation from, 645–650 mechanism of, 522
radical addition reactions of, 1031–1034 reagents for, 521, 524–525
Alder rule, 840–841 regioselectivity of, table, 523
aldol reaction, 682 steric effects in, 523
acid-catalyzed mechanism, 683 thermal reversibility of, 524–525
analysis by Marcus equation, 283–285 hydroboration-oxidation of, 187–188
base-catalyzed mechanism, 683 hydrobromination, radical
directed, 687 examples of, 1036
kinetic control in, 688–689 regiochemistry of, 1027
stereochemistry of, 688–692 stereochemistry, 1027–1028
enantioselective catalysts for, 695–697 hydrohalogenation, 474, 476–482
examples of, 682 by radical addition, 1026–1028
kinetics of, 284–5, 685 stereochemistry of, 478–479
mixed aldol reaction, 685–686 oxymercuration of, 515–520
regioselectivity of, 686 relative rates for, table, 516
stereoselectivity of, 685 substituent effects in, 518–520
silyl ketene acetals as nucleophiles in, 697 photochemical cycloadditions, 1109–1111
silyl ketene thioacetals as nucleophiles in, 697 with aromatic compounds, 1135–1137
thermodynamic control in, 690 with carbonyl compounds, 1132–1134
alkanes photochemical isomerization of, 1081–1090
bond orders for, 77 composition of photostationary state, 1082
computation of enthalpy of formation by MO of ethene, 1082–1083
methods, 52 of stilbene, 1085–1090
conformation of, 142–145 of styrene, 1083–1085
molecular graphs for, 64 photochemical reactions of, 1091–1096,
alkenes 1109–1111
bridgehead, synthesis by intramolecular examples, 1111
Diels-Alder reactions, 871 radical addition reactions, 1004–1008
bromination, 482–497 of aldehydes, 1031, 1034
bromonium ion intermediates in, 486 examples, 1033–1036
mechanism of, 492 of formamide, 1032–1033
reagents for, 491 of halomethanes, 1029–1031