Page 1190 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

methyl, 300 photochemical reactions of, 1116–1132 1177
electron distribution in, 65 cycloaddition with alkenes, 1132–1134
methylcyclohexyl, 430–431 type-II cleavage, proton affinity of, 636 Index
norbornyl, 422, 448–452 -cleavage, 1118, 1120–1122, 1124
observation of, 436–438 reactions with organometallic reagents, 676–682
pentadienyl stereoselectivity of, 680–682
electrocyclization of, 908–909 reduction, 176–179
in petroleum processing, 454–459 by sodium borohydride, 633–634
phenalenyl, 757 enantioselective, 193–196
phenonium, 425 relative reactivity of, 319–323, 632–637
phenyl, 436, 817 resonance effects in, 320–321
rearrangement of, 440–447, 480 substituent effects in, 320–322
resonance in, 22, 301–302, 433 substitution reactions of, 629, 654–668
stability of, 300, 426–429 acylation of alcohols, 664–667
table, 427 amide hydrolysis, 662–664
structure of, 430–433 ester aminolysis, 659–662
substituent effects on, 304–305, ester hydrolysis, 654–658
432–434, 632 intramolecular catalysis of, 668–676
substitution versus elimination, 437–439 tetrahedral intermediates in, 630
trichloromethyl, 434 unsaturated
trifluoromethyl, 434 conformation of, 151
vinyl, 435–436 excited states of, 1117–1118
-alkoxy, 22 photocycloaddition reactions with alkenes,
carbodiimides 1125–1126
in acylation reactions, 667 photoreactions of, 1123–1124
carbon resonance of, 21
electronegativity of, 12–14 carboxylic acid anhydrides
carbonium ions, 456–458 rate of hydrolysis, 328
structure of, 458 carboxylic acid derivatives, see also acyl chloride,
carbon monoxide acid anhydrides, etc.
electron density by Laplacian function, 94 acylation reactions of, 664–668
carbon tetrachloride, see halomethanes reactivity toward organometallic compounds, 677
carbonyl addition reactions relative reactivity of, 636
acid and base catalysis of, 345, 630 substitution reactions of, 654–668
mechanisms of, 325–327 carboxylic acids
nucleophilic, intermediates in, 319–331 acid dissociation constants, computation of, 53
radical, comparison of rates with alkenes, derivatives, relative reactivity of, 328
1007–1008 substituent effects on acidity, 13, 53–54, 105,
tetrahedral intermediate in 322
evaluation of relative stability, 329–30 CAS MO method, 36
carbonyl compounds, see also aldehydes, esters, catalysis, 345–358
ketones, etc. by acids and bases, 345–353
acetal formation, 640 by Lewis acids, 354–358
addition reactions of, 629–632 intramolecular in carbonyl substitution reactions,
with enolates and enols, 682–697 668–676
with organometallic reagents, 676–682 nucleophilic
condensation reactions of, 629, 645–653 in ester hydrolysis, 657
with nitrogen nucleophiles, 645–653 catalytic hydrogenation, see hydrogenation
conformation of, 148–149 catalytic reforming, 454–456
cyanohydrin formation from, 635 catalytic triad in enzymatic hydrolysis, 675–676
enolization of, 601–608 catechol borane
excited states of, 1116–1117 hydroboration by, 525
charge distribution and bond order, 1117 CBS catalysts, see also oxazaborolidines
structure, 1116–1117 for enantioselective reduction of ketones,
hydration of, 638–639 194–196
acid and base catalysis of, 639 CBS MO method, 36
equilibrium constants for, table, 329, 638 CD, see circular dichroism
interaction with Lewis acids, 323, 636–637, chain reaction, definition, 965
848–849 chain length of, 965, 993