Page 1210 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

stereoisomer, definition, 117 on radical stability, 311–318, 986–988 1197
stereoselective reactions on reaction intermediates, 297–299
1,3-dipolar cycloaddition, 878–879 substituent groups Index
catalytic hydrogenation, 170–176 electronegativity of, table, 102, 260
Diels-Alder reaction, 839–842 hardness of, table, 102
enolate alkylation, 615–619 subtilisin
examples of, 170–182 enzymatic resolution by, 141, 222
hydride reduction of ketones, 176–179 sulfenylation of alkenes, 497–500
hydroboration, 188, 524–525 regioselectivity of, 499
nucleophilic addition to acyclic ketones, 179–182 sulfides
stereoselectivity, 119, 169 as nucleophiles in S RN 1 reactions, 1050
stereospecificity, 169 sulfinyl substituents, 299
stereospecific reactions sulfonate groups
1,3–dipolar cycloaddition, 877–8 internal return in solvolysis, 397–398
bromination of alkenes, 183–185 as leaving groups in nucleophilic substitution,
Diels-Alder reaction, 839–840 413–414
examples of, 183–188 sulfones
steric approach control, definition, 177 vinyl as dienophiles and synthetic equivalents,
in additions to acyclic ketones, 180 862–863
in hydride reduction of cyclic ketones, 177–178 sulfonium ylides
steric effects allylic, [2,3]-sigmatropic rearrangement of, 942
in Diels-Alder reactions, 843 sulfonyl group
in enolate alkylation, 615–619 effect on cyclization of 5-hexenyl radical, 1012
in Friedel-Crafts acylation, 812 substiuent effect of, 299
in nucleophilic substitution, 415–417 sulfoxides
on reactivity, 297 acidity of, 589
on regiochemistry of elimination reactions, allylic
562–563 2,3-sigmatropic rearrangement of, 940
stilbene chirality of, 129
E and Z isomers vinyl, as dienophiles, 863
absorption spectra, 1087 sulfuranes
ground state structure, 1086 as intermediates in sulfenylation of alkenes, 498
photocyclization of, 1091 sulfur-containing groups
photoisomerization of, 1085–1090 carbanion stabilization by, 599
rotational energy profile for excited states, 1090 ylides, 600–601
strain sultams
1,3-allylic, 147 camphor, as chiral auxiliaries, 207–208
in cycloalkanes, 86–88, 161–166 suprafacial, definition, 911–912
from molecular mechanics, 167–168 symmetry, see orbital symmetry, molecular
torsional, 143, 153 symmetry
van der Waals, 78, 143–144, 154 synchronicity
styrene and derivatives of 1,3-dipolar cycloadditions, 882
excited states of, 1083–1085 definition, 852
hydration reactions of, 482–483 of Diels-Alder reaction, 852
reactivity toward selenenylation, 501
synthetic equivalent, definition, 862
substituent constants, Hammett, 338–339
table, 340
substituent effects TADDOLS, see
on [3,3]-sigmatropic rearrangements, 924–927, tetraaryl-1,3-dioxolane-4,5-dimethanols
932, 937 tartrate esters
on carbanion stability, 309–311, 591–594 as chiral ligands for enantioselective
on carbocation stability, 304–305, 432–434 epoxidation, 197–199
comparison of gas phase and solution phase, 344 termination, in radical reactions, 965, 992–994
DFT formulation of, 100–105 tetraaryl-1,3-dioxolane-4,5-dimethanols derivatives
in Diels-Alder reactions, 843–848 as enantioselective catalysts
directive, in catalytic hydrogenation, 171–176 for 1,3-dipolar cycloaddition, 868
in electrophilic aromatic substitution, 779–787 for Diels-Alder reactions, 888
on nucleophilic substitution, 418–419 tetrabromomethane, see halomethanes
on radical reactivity, 1004–1007 tetrahedral intermediate