Page 1330 - Advanced Organic Chemistry Part B - Reactions & Synthesis

solvent, 18 stereochemistry of, 528 1307
in hydride reduction of halide, 422 synthetic applications, 531–534
in nucleophilic substitution, 224 Dipolarophiles, 527 Index
N N-dimethylpropyleneurea, as solvent, 18 1,3-dipoles
enolate reactivity, effect on, 20 azomethine ylides as, 532
Dimethyl sulfoxide (DMSO) examples, 528
as solvent in, 18 nitrile oxides as, 532
amine oxide elimination, 597 nitrones as, 532, 535–536
bromohydrin synthesis, 301–302 oxazolium oxides as, 530
hydride reduction of halides, 422 3-oxidopyridinium betaines as, 530
nucleophilic substitution, 224 Discodermolide, multistep synthesis, 1231–1245
oxidation by, 1070–1072 allenylstannanes in, 1235
Dimethylsulfonium methylide, 177 allylsilanes in, 1239
reaction with alkyl halides, 181 boron enolates in, 1238
Dimethylsulfoxonium methylide, 177 chiral auxiliaries in, 1236
Vic-diols scale-up of, 1243
oxidative cleavage, 1126–1128, 1144–1145 Disiamylborane, see Borane, derivatives,
periodate, 1144 bis-(1,2-dimethylpropyl)
lead tetraacetate, 1144–1145 1,3-dithiolanes
pinacol rearrangement of, 883–890 as carbonyl protective groups, 274
reduction to alkenes, 450 reductive desulfurization of, 453–454
synthesis by 1,3-dithianes, 274
dihydroxyation of alkenes, 1074–1075 as carbonyl protective groups, 274
reductive coupling of carbonyl compounds, as nucleophilic acyl equivalents, 1168
444–447 DMAP, see N N-dimethylaminopyridine
Dioxaborolanes DMF, see N N−dimethylformamide
as chiral catalyst for cyclopropanation, 933 DMPU, see N N-dimethylpropyleneurea
Dioxaborolones DMSO, see Dimethyl sulfoxide
chiral catalyst for aldol reaction, 126–127 Double stereodifferentiation
Dioxiranes, epoxidation of alkenes by, in aldol reactions, 108–114
1097–1103, 1113 examples, 111–114
enantioselective, 1102–1103 in allylboration, 804–805
substituent effects on, 1098–1100 in allylstannation, 843–847
1,3-dioxolanes DPPA, see Diphenylphosporyl azide
directing effect in cyclopropanation, 920
as protecting groups, 266, 273 (Eap) 2 CCl, see Bis-(iso-2-ethylapopinocamphyl)
initiation of polyene cyclization by, 865, 867 chloro
vinyl, as dienophiles in Diels-Alder EE, see 1-ethoxyethyl
reactions, 493 Effective atomic number, 769
DIPAMP, see Bis-1,2-[(2-methoxyphenyl) Elimination reactions
phenylphosphino]ethane amine oxides, 345, 581, 598, 1088
Bis-(2,2’-diphenylphosphinyl)-1,1’-binaphthyl cheletropic, 591–593
(BINAP) sulfolene dioxides, 591
ligand in homogenous hydrogenation, esters, 600–601
377–378, 383 examples of, 598, 601
Diphenylphosporyl azide -hydroxyalkylsilanes, 171–172
as reagent for reductive, 681, 687
amide formation, 254–255 selenoxides, 581–582, 598–599
curtius rearrangement, 948 sulfoxides, 598–599, 602
synthesis of azides, 232 thermal, 590–604
1,3-dipolar cycloadditions, 526–538 xanthates, 601, 603–604
enantioselective catalysts for, 536–538 Enamines
nickel-box complexes as, 537 alkylation of, 31, 47–48
TADDOL complexes as, 537 examples, 54
examples, 533–534 conjugate addition reactions of, 193
FMO analysis, 529 [2 + 2] cycloaddition, 538, 542
intramolecular, 532 formation of, 46
Lewis acid catalysis of, 535–538 halogenation, 330
regioselectivity of, 528–531 as nucleophiles, 1, 46