Page 1197 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1184 enthalpy of reaction, 253 A AL 1 mechanism, 656
calculation of, 258–259 B AC 2 mechanism, 654
Index determination of, 271 computational model for, 325–326
examples of, 273 intramolecular catalysis of, 670–674
relation to reaction rates, 269–270 leaving group effects on, 655
entropy of reaction, 253 mechanism of, 324–326, 654–656
determination of, 271 nucleophilic catalysis of, 657
examples of, 273–274 solvent effects on, 365–366
for solvolysis of t-butyl chloride, 273 of tertiary alcohols, 656
enzymes rate of hydrolysis, 328
alcohol dehydrogenase, 135 reactions with organometallic compounds, 678
epoxide hydrolases, 224–227 effect of TMEDA, 678
hydrolytic, 875–876 E T (30), as measure of solvent polarity, 360
lipases, 216–221 ethane
proteases, 222–224 conformation of, 78–81, 142–143
in resolution of enantiomers, 215–227 electron density by Laplacian function, 93–94
stereoselective reactions of, 133–136 rotational barrier in, 78–81
epoxidation ethenamine
of alkenes, 503–511 electron density distribution in, 73–74
by dimethyldioxirane, 507–510 electrostatic potential surface for, 73–74
hydroxy group directing effects in, 505–506 MOs of, 47
mechanism of, 504 resonance in, 22
reagents for, 503–504, 510–511 ethene
substituent effect on, 504, 506–508 electron density by Laplacian function, 93
transition structures for, 507–508 MOs of, 39–42, 46–47
Sharpless asymmetric, 196–199 photocycloaddition with benzene
computational model for, 198–199 computational modeling of, 1136–1137
epoxides photodimerization of
enzymatic hydrolysis of, 224–227 computational modeling, 1109–1110
ring-opening of, 186–187, 511–512 photoexcited states of, 1082–1083
pH-rate profile for, 512 reaction with ozone, 49–50
regioselectivity of, 511–512, 515 stabilization by substituents, 52
stereochemistry of, 513–515 substituted
ESR, see electron spin resonance electron density distribution , 71–73
esterases, see also hydrolases electrostatic potential surface , 74–75
pig liver esterase ethers
in resolution of enantiomers, 217–220 allyl phenyl, sigmatropic rearrangement of,
selectivity model for, 217–220 934–935
in resolution of enantiomers, 216–221 allyl vinyl, sigmatropic rearrangement of, 273,
esterification 933
by acylation of alcohols, 664–668 autoxidation, 1026
enzymes as catalysts for, 216, 223 neighboring group participation, 421
esters -halo, effect of hyperconjugation on reactivity,
aminolysis, 659–662 84–85
catalysis by 2-pyridone, 661–662, 673–674 ethylene, see ethene
general base catalysis of, 659 ethyl radical
leaving group effects on, 661 ESR spectrum of, 971
rate of, 328 ethyne
enolates of electron density by Laplacian function, 93
in aldol reactions, 692–694 excited states of
boron, 693 1,3-cyclohexadiene, 1106
formation of, 937 benzaldehyde, 1118
solvent effects on, 937 ethene, 1082–1083
formation stilbene, 1085–1090
by Fischer esterification, 664 styrene, 1083–1085
from acid anhydrides, 665
from acyl halides, 665–666 Felkin-Ahn model, 179, 234
hydrolysis, 654–656 for addition reactions with carbonyl
A AC 2 mechanism, 654 compounds, 680