Page 1201 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1188 kekulene, 735–736 kinetic isotope effect, 332–335
ketenes in benzylic bromination, 1021–1022
Index [2+2] cycloaddition reactions of, 835 determination of, 334–335
intramolecular, 890–891 in diazonium coupling, 814
orbital array for, 888–889 in Diels-Alder reaction, 851
stereoselectivity of, 890 in electrophilic aromatic substitution, 777
transition structure for, 889 bromination, 803
formation from acyl halides, 666 table of, 790
synthetic equivalents for in Diels-Alder reaction, in elimination reactions, 552
862 examples of, 334
ketones, see also carbonyl compounds primary, 332–333
acidity of, 592–593 secondary, 333
acyclic solvent, 347
conformation of, 148–149 kinetics
stereoselective reduction of, 179–182 of chain reactions, 992–995
addition reactions of, 629–632 integrated rate expressions, 280–285
alcohols, 640 Michaelis-Menten, 140
hydride reducing agents, 176–181, 633–634 rate expressions
of organometallic reagents, 680–682 for addition of hydrogen halides to alkenes,
cyclic 478
relative reactivity of, 634–635 for aldol reactions, 284–285, 685
stereoselective reduction of, 176–179 aromatic chlorination, 801
enantioselective reduction of, 193–196 for bromination of alkenes, 486
enolate formation from, 592–595 chain reactions, 993–994
kinetic control of, 287, 595 examples of, 283–285
stereoselectivity of, 597 for Friedel-Crafts acylation, 811
enolization of, 601–608 for Friedel-Crafts alkylation, 805–806
equilibrium constants for, table, 604 for nitration, 796–797
hydration, 638–639 for nucleophilic substitution, 391, 393–394
photochemical reactions of, 1116–1132 reaction order, 280
decarbonylation, 1120–1122 steady state approximation, 282, 993
photoenolization, formation of Kohn-Sham equation, 54
benzocyclobutenols by, 1120 -lactams, see azetidinones
type-II cleavage, 1122
-cleavage, 1118, 1120–1122, 1124
reactions with organometallic compounds, lactones
676–682 formation by 8-endo cyclization, 1014
chelation in, 680–682 ring size effect in formation, 422
stereoselectivity of, 680–682 lanthanides
reduction of as chiral shift reagents, 208–209
electrostatic effects in, 238 Laplacian representation of electron density, 92–94
polar effects on, 234–239 in cyclopropane, 86–87
reductive photodimerization, 1119–1120 LCAO, see linear combination of atomic orbitals
relative reactivity of, 633–634 leaving groups
towards NaBH 4 , 633 in aromatic nucleophilic substitution, 817–819
synthesis in elimination reactions, 558
by hydration of alkynes, 544 in nucleophilic substitution
using organoboranes, 528 reactivity of, 413–415
unsaturated table of, 414, 415
conformation of, 151–152 in relation to enolate alkylation, 614–615
cyclic, photochemical reactions of, Lewis acids
1125–1129 as catalysts, 355–358
photochemical cycloaddition reactions, in 1,3-dipolar cycloaddition, 886–888
1125–1126 in aromatic nitration, 797
photochemical deconjugation of, 1124 in Diels-Alder reactions, 848–850
ketyl radicals, 991 in radical cyclization, 1013, 1039
kinetic acidity, 581 chelation of, 354–355
kinetic control of product composition, 285–287 effect on carbonyl 13 C chemical shfts, 357
of enolate formation, 287 empirical measures of, 357–358