Page 1329 - Advanced Organic Chemistry Part B - Reactions & Synthesis

1306 Diazo compounds (Cont.) examples, 496–498
carbenes from, 909–913 LiClO 4 as, 485
Index esterification by, 227 MABR as, 500
in formation of sulfonium ylides, 583–584 Sc (O 3 SCF 3 3 as, 486
ring expansion reaction with cyclic ketones, N-trimethylsilyl-bis-
891–892 trifluoromethanesulfonamide
synthesis of, 909–911 as, 486
Diazo transfer reaction, 911–912 masked functionality in, 491–493
Diazonium ions, alkyl regioselectivity, 475–476
rearrangement of, 890–892 secondary orbital interactions in, 478
Diazonium ions, aromatic stereochemistry of, 474–478
phenyl cations from, 1028 steric effects in, 479–480
substitution reactions of, 1027–1035 substituent effects on, 475–481
copper-catalyzed, 1032 synthetic applications, 487–499
mechanism of formation, 1028 synthetic equivalents in, 491–493
reductive, 1029–1030 transition structures for, 482–484
synthesis of using electron transfer in, 483–484
azides, 1032 1,5-dienes
fluorides, 1031 hydroboration in multistep synthesis, 1198
halides, 1030–1032 [3,3]-sigmtropic rearrangement of, 552–560
iodides, 1031–1032 Dienes
phenols, 1030 in Diels Alder reactions
DEAD, see Diethyl azodicarboxylate pyridazines as, 595
Dehalogenation pyrones as, 490–491
reductive, 458 quinodimethanes as, 489–490, 592
Dehydrobenzene, see Benzyne 1,2,4,5-tetrazines as, 595–596
Diamines 1,2,4-triazines as, 595
chiral, as ligands in alkene reaction with singlet oxygen, 1124
dihydroxylation, 1081 synthesis from
DiBAlH, see Disobutylaluminum hydride alkene-alkyne metathesis, 764–765
Diborane, see also hydroboration sulfolene dioxides, 591–592
as reducing agent, 400, 404–405 Dienophiles in Diels-Alder reactions
Dicyclohexylcarbodiimide (DCCI) benzyne, 1041
acylation of alcohols, 247 nitroalkenes, 492
acylation of amines, 253 quinones, 494, 506–507, 512, 517
co-reagent in dmso oxidation, 1070 vinyl boronates, 526
macrolactonization, 249 vinyl dioxolanes, 493
polypeptide synthesis, 1247 vinyl phosphonium ions, 493
Dieckmann condensation, 150 vinyl sulfones, 492
Diels-Alder reaction, 474–526 Diethyl azodicarboxylate (DEAD)
alder rule, 478–480 in Mitsunobu reaction, 221
chiral auxiliaries for, 499–504 Diimide
enantioselective catalysts for, 505–518 alkenes, reduction by, 388–390
examples, 495, 497–498, 502, 514, examples, 389
521–522 DiPCI, see Diisopropylcarbodiimide
FMO interpretation, 474–477 Disobutylaluminum hydride
intramolecular, 518–526 reduction of
bifunctional Lewis acid catalysis of, 520 amides, 270
copper BOX complexes in, 514 esters, 401–402
examples, 523–524 nitriles, 402–403
Lewis acid catalysis of, 519–520, 526 enones, 407
tethers for, 525–526 Diisopropylcarbodiimide
vinyl boronates in, 526 in acylation of alcohols, 245
inverse electron demand, definition, 475 N N-dimethylaminopyridine (DMAP)
Lewis acid catalysis of, 481–487 as catalyst for alcohol acylation, 244
bifunctional, 494, 519 in macrolactonization, 249
computational model of, 482–484 N N−dimethylformamide (DMF)
copper BOX complexes, 508–510, 514 hydrogen atom donor in dediazonization,
diethylaluminum chloride as, 517 1029–1030