Page 1193 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1180 1,3,5,7-cyclooctatetraene in aldol reactions, 683–685
dianion of, 741–742, 990 delocalization energy, definition, 19
Index dication of, 742 as a criteria of aromaticity, 715
photochemistry of, 1144 estimation of, 30
properties of, 727–728 density functional theory
cyclooctene application to properties and reactivity, 94–105
E-isomer, chirality of, 131 B3LYP method, 55–57
photoreactions of, 1094 concepts, application to cycloaddition reactions,
cyclopentadiene 947–951
acidity of, 740 electron density functionals, 54–57
derivatives, sigmatropic shifts in, 917 interpretation of substituent effects by, 100–105
Diels-Alder reactions of, 840–841, 843 Kohn-Sham equation, 54
cyclopentadienyl anion Dewar benzene, see bicyclo[2.2.0]hexa-2,5-diene
aromaticity of, 32, 740 DFT, see density functional theory
cyclopentadienyl cation, 739–740 DHQ, see quinoline alkaloids
cyclopentane derivatives DHQD, see quinoline alkaloids
conformation of, 162–163 diamines
pseudorotation in, 163 intramolecular catalysis by, 675
cyclopentene diaminomethane, conformation, 84
photocycloaddition with cyclohexenone, diamond lattice, as conformational framework, 166
1125–1126 diastereomers, definition, 126–127
photoreactions of, 1095 diastereotopic, definition, 134
cyclopentenone relationship to NMR spectra, 134–135
photochemical reactions of, 1125 diazoalkanes
cyclopropane as 1,3-dipoles, 875, 878–879
bonding in, 85–87 relative reactivity of, table, 877
divinyl, Cope rearrangement, 929 frontier orbitals of, 880–881
electron delocalization in, 86–87 diazonium ions
hybridization in, 86 alkyl
protonated nucleophilic substitution reactions of, 405–407
in carbocation rearrangements, stability of, 68
441–443 aryl
structure of, 162 as electrophiles in aromatic substitution,
vinyl, thermal rearrangement, 929 813–814
cyclopropenium cation, 738–739 benzyl, in electrophilic aromatic substitution, 808
cyclopropyl cation methyl, charge distribution in, 66
electrocyclic ring opening of, 907–908 -dicarbonyl compounds
cyclopropyl halides enolization of, 606
S RN 1 substitution reactions, 1051 -dicarbonyl compounds
cyclopropylmethyl cation, 427 acidity of, 592
cyclopropylmethyl radical enolization of, 603-606
generation of, 972 Diels-Alder reaction, 839–873
potential energy profile for, 974 as an indicator of aromatic stabilization, 748–749
ring opening of, 973–974, 1008–1009 application of DFT concepts to reactivity,
945–950
in comparison with frontier MO theory, 949
decahydronaphthalene, see decalin softness matching for regioselectivity, 948
decalin catalysis by Lewis acids, 356, 848–850
conformations of, 159–160 chiral auxiliaries for, 865–866
decarbonylation enantioselective, 865–868
of acyl radicals, 967 examples of, 861
of ketones, photochemical, 1120–1122 intramolecular, 868–873
decarboxylation conformational factors in, 869–870
Of acyloxy radicals, 967, 979–980 examples of, 872–873
degenerate rearrangements, 930–931 inverse electron demand, 843
dehalogenation of isobenzofuran derivatives, 760, 858, 864
stereochemistry of, 564–565 kinetic isotope effect in, 335
dehydration of polycyclic aromatic hydrocarbons, 748–749,
of alcohols, 474, 564–565 857–858