Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis : Novel ...

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N O OBu t N O THF,−78°C, 1 h OBu t 97% OMe Li 94% N OH OBu t ButO But OMe O O + − − O + − O N + Bn 292 H THF,−78°C, 1 h M Li OMe Bu t O N OH c = 0.05 M Scheme 2.182 O O N O HO N Bn O O OBu t NITRONE REACTIONS 279 CH 2Cl 2, r.t., 5 d c = 0.05 M OBu t OMe CH 2Cl 2, r.t., 5 d NHBn OMe O O N O HO N Bn 408a 408b 409b Scheme 2.183 + + O i O OBu t OMe NHBn 409a i: Zn, Cu(OAc),AcOH, 70˚C, 1 h
280 NITRONES: NOVEL STRATEGIES IN SYNTHESIS Table 2.15 Diastereoselective addition of vinyl reagents to nitrone BIGN 292 Lewis Yield Entry M (eq) acid a Solvent (t 0 ) Time syn/anti b (%) c 1 MgBr (1.2) none THF (0 ◦ C) 1 h 76:24 86 2 MgBr (1.2) ZnBr2 Et2O (0 ◦ C) 1 h 53:47 84 3 MgBr (1.2) MgBr2 Et2O (0 ◦ C) 1 h 56:44 80 4 MgBr (1.2) Et2AlCl Et2O (0 ◦ C) 1 h 8:92 86 5 CeCl3 (1.2) none THF (−40 ◦ C) 2 h 58:42 74 6 CeCl3 (1.2) Et2AlCl THF (−40 ◦ C) 2 h 30:70 78 7 (CuLi)1/2 (1.0) none THF (−80 ◦ C) 2 h 70:30 80 8 (CuLi)1/2 (1.0) Et2AlCl THF (−80 ◦ C) 2 h 22:78 79 9 Li (1.5) none THF (−80 ◦ C) 15 min 35:65 90 10 Li (1.5) Et2AlCl Et2O (−80 ◦ C) 15 min 4:96 92 11 AlEt2 (1.1) none Et2O (−40 ◦ C) 2 h 52:48 86 12 AlEt2 (3.0) none Et2O (−40 ◦ C) 2 h 32:68 87 a Nitrone was precomplexed with 1.0 eq of the Lewis acid prior to the addition. b Measured from the intensities of 1 H NMR signals. c Determined on isolated mixtures of syn and anti adducts. High stereoselective addition of vinylmagnesium bromide to L-tartaric acidderived nitrone was used as a key step in the synthesis of ( + )-lentiginosine and its structural analogs (653). It was shown (654) that the sequence terminal alkyne hydrozirconation, Zr to Zn exchange and addition to nitrones, is a good method to the stereoselective synthesis of (E)-N-allylhydroxylamines, under mild conditions and in good yield. Another useful method for generating various N -allylhydroxylamines is the reaction between vinyl boronic ester of pinacol and nitrone in the presence of dimethylzinc (655). Addition of lithium derivatives of acetylenides (Li—C≡C–CO2R) to chiral nitrones proceeds with high stereoselectivity, giving α-acetylene substituted hydroxylamines (410a,b) (656). This reaction has been successfully applied to the synthesis of γ-hydroxyamino-α,β-ethylene substituted acids (411a,b), formed in the reduction of (410) with Zn in the presence of acid (657, 658), and to chiral 5-substituted-3-pyrroline-2-ones (412a,b) (Scheme 2.184) (658). Similar addition reactions of alkyl 3-lithiopropiolates to nitrones with subsequent Raney Ni hydrogen reduction and amino group protection, led to the synthesis of (S) and (R)-vigabatrin (659). Addition of (trimethylsilyl)acetylides to chiral α-aminoalkyl- (413) and α-alkoxyalkyl-(BIGN) (292) nitrones proceeds stereoselectively. Successive desilylation (Bu4NF, THF) and transformation of the ethynyl group into carboxyl (RuCl3-NaIO4) led to the synthesis of diastereomerically pure N -hydroxy-αamino acids (414) andα-amino acids (415) (Scheme 2.185) (199, 202, 652, 660).
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NITRILE OXIDES, NITRONES, AND NITRO
Page 6 and 7:
NITRILE OXIDES, NITRONES, AND NITRO
Page 8:
CONTENTS Series Foreword vii List o
Page 12 and 13:
LIST OF ABBREVIATIONS AIBN 2,2’-a
Page 14:
LIST OF ABBREVIATIONS xi RC radical
Page 17 and 18:
2 NITRILE OXIDES + − − + + −
Page 19 and 20:
4 NITRILE OXIDES NaOHa1 R-CH=NOH Na
Page 21 and 22:
6 NITRILE OXIDES ammonium nitrate (
Page 23 and 24:
8 NITRILE OXIDES R O N N R′ N NO
Page 25 and 26:
10 NITRILE OXIDES HON C(NO 2) Me Me
Page 27 and 28:
12 NITRILE OXIDES which rapidly eli
Page 29 and 30:
14 NITRILE OXIDES Dimethyl furoxan-
Page 31 and 32:
16 NITRILE OXIDES R2P(O)C=NOH N(CH2
Page 33 and 34:
18 NITRILE OXIDES obtained by the s
Page 35 and 36:
20 NITRILE OXIDES (136, 137), appli
Page 37 and 38:
22 NITRILE OXIDES RCNO + R′CH=CH2
Page 39 and 40:
24 NITRILE OXIDES aldehydes are bei
Page 41 and 42:
26 NITRILE OXIDES R Cr(CO)3 Ar = 3,
Page 43 and 44:
28 NITRILE OXIDES bonding effect. T
Page 45 and 46:
30 NITRILE OXIDES Selective nitrile
Page 47 and 48:
32 NITRILE OXIDES H H H RCNO + R =
Page 49 and 50:
34 NITRILE OXIDES O O O Br ArCNO Ar
Page 51 and 52:
36 NITRILE OXIDES the bridgehead po
Page 53 and 54:
38 NITRILE OXIDES O O OR′ H H 94
Page 55 and 56:
40 NITRILE OXIDES H O N H O O R 101
Page 57 and 58:
42 NITRILE OXIDES O O 111 CH(OMe)2
Page 59 and 60:
44 NITRILE OXIDES Ph2CHCO N H2C N M
Page 61 and 62:
46 NITRILE OXIDES O (Me 2CHO) 2P N
Page 63 and 64:
48 NITRILE OXIDES R 137a-f PhCNO N
Page 65 and 66:
50 NITRILE OXIDES R N Ph N O O Ph R
Page 67 and 68:
52 NITRILE OXIDES derivatives 4-R 2
Page 69 and 70:
54 NITRILE OXIDES OH N H (CH2)n R N
Page 71 and 72:
56 NITRILE OXIDES Ar R 1 N 174 N O
Page 73 and 74:
58 NITRILE OXIDES N-benzyladamantyl
Page 75 and 76:
60 NITRILE OXIDES Ph3P L Rh O 194 N
Page 77 and 78:
62 NITRILE OXIDES and modern prepar
Page 79 and 80:
64 NITRILE OXIDES R 2 = MeO2C, R 3
Page 81 and 82:
66 NITRILE OXIDES 223 with 2-iodoni
Page 83 and 84:
68 NITRILE OXIDES N O O N N N R R R
Page 85 and 86:
70 NITRILE OXIDES complexes [PdCl2(
Page 87 and 88:
72 NITRILE OXIDES measured for the
Page 89 and 90:
74 NITRILE OXIDES Oxidation of (alk
Page 91 and 92:
76 NITRILE OXIDES electrophiles as
Page 93 and 94:
78 NITRILE OXIDES O 2N Ph R S N ONC
Page 95 and 96:
80 NITRILE OXIDES PhCH 2Co(dmgH) 2p
Page 97 and 98:
82 NITRILE OXIDES are formed exclus
Page 99 and 100:
84 NITRILE OXIDES On treatment with
Page 101 and 102:
86 NITRILE OXIDES PhSO 2 R R′C=NO
Page 103 and 104:
88 NITRILE OXIDES R X = OTMS O O H
Page 105 and 106:
90 NITRILE OXIDES TBSO H Me NOH TBS
Page 107 and 108:
92 NITRILE OXIDES A synthetic appro
Page 109 and 110:
94 NITRILE OXIDES N O H CO 2Me H 2N
Page 111 and 112:
96 NITRILE OXIDES the unambiguous a
Page 113 and 114:
98 NITRILE OXIDES t-Bu t-Bu O O O O
Page 115 and 116:
100 NITRILE OXIDES COX-2 selectivit
Page 117 and 118:
102 NITRILE OXIDES elastase release
Page 119 and 120:
104 NITRILE OXIDES ambient temperat
Page 121 and 122:
106 NITRILE OXIDES HO Ph O N O O N
Page 123 and 124:
108 NITRILE OXIDES and acceptor sub
Page 125 and 126:
110 NITRILE OXIDES 31. Belen’kii
Page 127 and 128:
112 NITRILE OXIDES 87. Matt Ch, Gis
Page 129 and 130:
114 NITRILE OXIDES 146. Faita G, Pa
Page 131 and 132:
116 NITRILE OXIDES 208. Gravestock
Page 133 and 134:
118 NITRILE OXIDES 266. Tian L, Xu
Page 135 and 136:
120 NITRILE OXIDES 324. Stajer G, B
Page 137 and 138:
122 NITRILE OXIDES 382. Himo F, Lov
Page 139 and 140:
124 NITRILE OXIDES 445. Yamamoto T,
Page 141 and 142:
126 NITRILE OXIDES 504. D’ Alelio
Page 144 and 145:
2 Nitrones: Novel Strategies in Syn
Page 146 and 147:
SYNTHESIS OF NITRONES 131 Treated w
Page 148 and 149:
R H OH R N R Oxone K2CO3 OH R N O S
Page 150 and 151:
H N H RO R N H N H CO2H OH O OR P O
Page 152 and 153:
R1 − − R N O 1-CH2-NH-R2 2 BF4
Page 154 and 155:
O N+ O − (EtO) 2P XCH2CN (X = Cl,
Page 156 and 157:
Et H3CO H 3CO − O R R N 1 H N H O
Page 158 and 159:
[O] SYNTHESIS OF NITRONES 143 N H N
Page 160 and 161:
(R 1 O)m O 47 ( )n OH + RNHOH (R 1
Page 162 and 163:
R 5 R 6 R 5 R 6 R6 R5 O R 1 R5 R R6
Page 164 and 165:
+ N O − (EtO)2(O)P HO (EtO)2(O)P
Page 166 and 167:
H O − N O 166, 167 AZN O N − +
Page 168 and 169:
AcO OAc OAc O OAc O OAc OAc O OAc O
Page 170 and 171:
SYNTHESIS OF NITRONES 155 Similarly
Page 172 and 173:
O Ph Et 2N R R 1 S CHO N COOEt R =
Page 174 and 175:
SYNTHESIS OF NITRONES 159 In a simi
Page 176 and 177:
SYNTHESIS OF NITRONES 161 (EtO) 2(O
Page 178 and 179:
R 2 R 1 Cl Ph O · Cl Ph N OR Ph N
Page 180 and 181:
R 1 NO2 R 2 PhSeH R 1 (EtO)2(O)PCH2
Page 182 and 183:
HO MeO2C Br "N-exo" O O O MeO2C 105
Page 184 and 185:
R O N H Ar * SeOTF CH 2Cl 2 R O N H
Page 186 and 187:
SYNTHESIS OF NITRONES 171 (where R
Page 188 and 189:
2 PhCH = NONa H 150 N OH + R 1 R 2
Page 190 and 191:
R 2 R 3 H R 1 R 1 R 2 N O + N OH 16
Page 192 and 193:
R 1 R 2 − O + N OOH R 1 R 2 O OMe
Page 194 and 195:
[R1R2C(NO2)] − + M R3 178 175 (R
Page 196 and 197:
R R R R 188 189 NHOH a: R = Me b: R
Page 198 and 199:
STRUCTURE AND SPECTRA OF NITRONES 1
Page 200 and 201:
R R H C N O + H 3C Bu t + C STRUCTU
Page 202 and 203:
I R 1 − O R 2 ( )n − ( )n N O
Page 204 and 205:
Bu t Ph O N OH − + H H H CF 3 Ph
Page 206 and 207:
Bu N t H O + + N N − − ROCCH2 O
Page 208 and 209:
STRUCTURE AND SPECTRA OF NITRONES 1
Page 210 and 211:
ELECTROCHEMICAL PROPERTIES AND EPR-
Page 212 and 213:
Page 214 and 215:
R 2 R 1 N O ELECTROCHEMICAL PROPERT
Page 216 and 217:
Page 218 and 219:
NITRONE COMPLEXES 203 radiolysis in
Page 220 and 221:
R 2 226a-c R 1 N O + O N − + −
Page 222 and 223:
R 2 R O C N 1 R2 R3 + R 1 , R 2 , R
Page 224 and 225:
OH _ O + N R 1 a: R 1 = Me, b: R 1
Page 226 and 227:
R Me Me Me Me H N H 259 O O 255a-c
Page 228 and 229:
NITRONE REACTIONS 213 2.6.2. Reduct
Page 230 and 231:
N + O − • + ClO 2 N O • H O C
Page 232 and 233:
H O + N DMPO H O N N 228-232 MeOH P
Page 234 and 235:
Ph H3CO H3CO Ph N O 276 N O 281 O
Page 236 and 237:
Ph N O N F • Ph + Ph F Ph R F Ph
Page 238 and 239:
Ph Ph O O + N O − 286 Rl,Et 3B be
Page 240 and 241:
Table 2.9 Electroreductive coupling
Page 242 and 243:
NITRONE REACTIONS 227 This reaction
Page 244 and 245: 295a Br I NaOH, MeOH NaOH, MeOH NaO
Page 246 and 247: H 3C R H3C N O − + O N CH3 CH 3 C
Page 248 and 249: H + O N B− − − − H N − BH
Page 250 and 251: H H X + O N H RLi O N E X = CH2, NC
Page 252 and 253: NITRONE REACTIONS 237 Nucleophilic
Page 254 and 255: O BnO Ph Et 2N O BnO H 317 O O HO N
Page 256 and 257: NH 2 NH 2 Boc N H2N N(OH)Bn Boc N P
Page 258 and 259: NITRONE REACTIONS 243 EtAlCl2, TiCl
Page 260 and 261: NITRONE REACTIONS 245 Addition of v
Page 262 and 263: HO R R R HO N Bn NHBoc NH 2 NHBoc N
Page 264 and 265: RCHO BocNHOH R 2 + + O N R1 − PhS
Page 266 and 267: BzlOOC + NH3 Cl i OH BzlO Cl Cl Bzl
Page 268 and 269: Table 2.12 Addition a of 2-lithiofu
Page 270 and 271: H 2N O BnO O OH O CO2H H2N O N H OH
Page 272 and 273: 353 b a BnO BnO 354 Bn N CHO OBn b
Page 274 and 275: Table 2.13 Addition of organolithiu
Page 276 and 277: R N O Cl 367 −O + N Bu t LDA, THF
Page 278 and 279: HO HO OH N N • Ph • O OH O HO P
Page 280 and 281: RO2C N O X • N O • N O N O •
Page 282 and 283: N O 373 N O a 374, 376, 377 R2 376
Page 284 and 285: + N O − HN HO O R1 S R2 R3 + Ph 1
Page 286 and 287: + R 1 N R2 O O R 1 N R 2 − R 1 R
Page 288 and 289: NITRONE REACTIONS 273 Table 2.14 Sy
Page 290 and 291: + Ph N O − Bn + O Et 3SiO MeO O H
Page 292 and 293: O O O N Pri OCOPh R Me Bn CO 2H NHC
Page 296 and 297: O O O O 292 O H N −O + Bn O HO N
Page 298 and 299: NITRONE REACTIONS 283 The reaction
Page 300 and 301: O − O O BnO O O + O − O − N P
Page 302 and 303: R 1 R 2 NH 2 COOH Br a: b: c: d: e:
Page 304 and 305: NITRONE REACTIONS 289 2.6.6.1.11. N
Page 306 and 307: NITRONE REACTIONS 291 Nucleophilic
Page 308 and 309: O − O O + NBoc− O NBoc N Bn 1.
Page 310 and 311: NITRONE APPLICATION IN RADICAL POLY
Page 312 and 313: REACTIONS OF DIPOLAR 1,3-CYCLOADDIT
Page 318 and 319: a b c d REACTIONS OF DIPOLAR 1,3-CY
Page 320 and 321: R REACTIONS OF DIPOLAR 1,3-CYCLOADD
Page 324 and 325: a REACTIONS OF DIPOLAR 1,3-CYCLOADD
Page 328 and 329: − REACTIONS OF DIPOLAR 1,3-CYCLOA
Page 344 and 345:
REACTIONS OF DIPOLAR 1,3-CYCLOADDIT
Page 346 and 347:
(a) REACTIONS OF DIPOLAR 1,3-CYCLOA
Page 348 and 349:
O HO REACTIONS OF DIPOLAR 1,3-CYCLO
Page 350 and 351:
Page 352 and 353:
Bn REACTIONS OF DIPOLAR 1,3-CYCLOAD
Page 354 and 355:
Page 356 and 357:
CO 2Me O O REACTIONS OF DIPOLAR 1,3
Page 358 and 359:
Page 360 and 361:
Page 362 and 363:
Page 364 and 365:
H H REACTIONS OF DIPOLAR 1,3-CYCLOA
Page 366 and 367:
Page 368 and 369:
Page 370 and 371:
Page 372 and 373:
Page 374 and 375:
Me REACTIONS OF DIPOLAR 1,3-CYCLOAD
Page 376 and 377:
Page 378 and 379:
Page 380 and 381:
Page 382 and 383:
O REACTIONS OF DIPOLAR 1,3-CYCLOADD
Page 384 and 385:
Page 386 and 387:
Page 388 and 389:
Ph Ph REACTIONS OF DIPOLAR 1,3-CYCL
Page 390 and 391:
− O Me REACTIONS OF DIPOLAR 1,3-C
Page 392 and 393:
Page 394 and 395:
Page 396 and 397:
Ph REACTIONS OF DIPOLAR 1,3-CYCLOAD
Page 398 and 399:
Page 400 and 401:
B C A Closed [5,6] adduct B B KINUG
Page 402 and 403:
KINUGASA REACTION ([2 + 2] CYCLOADD
Page 404 and 405:
O O N N N O R R O O L 1 : N N N 1 m
Page 406 and 407:
R 1 R 1 O + N 774 a-e Δ O N N Ph 1
Page 408 and 409:
783 784 + N O + CH3 − N O Ph CH3
Page 410 and 411:
R 1 NHOH 793 + R 2 CHO 794 Hydroxyl
Page 412 and 413:
REACTIONS WITH CYCLOPROPANES 397 O
Page 414 and 415:
REFERENCES 399 properties and synth
Page 416 and 417:
REFERENCES 401 (d) Mottley C, Mason
Page 418 and 419:
REFERENCES 403 46. Sankuratri N, Ja
Page 420 and 421:
REFERENCES 405 105. Saladino R, Ner
Page 422 and 423:
REFERENCES 407 159. Sridharan V, Mu
Page 424 and 425:
REFERENCES 409 205. Cupone G, De Ni
Page 426 and 427:
REFERENCES 411 259. Balasundaram B,
Page 428 and 429:
REFERENCES 413 310. (a) Cicchi S, M
Page 430 and 431:
REFERENCES 415 (b) Creary X. Acc. C
Page 432 and 433:
REFERENCES 417 410. Dziembowska T,
Page 434 and 435:
REFERENCES 419 459. Bourquet E, Ban
Page 436 and 437:
REFERENCES 421 Papers of 6-th Inter
Page 438 and 439:
REFERENCES 423 573. Ok D, Fisher MH
Page 440 and 441:
REFERENCES 425 636. (a) Jost S, Gim
Page 442 and 443:
REFERENCES 427 690. Haire DL, Janze
Page 444 and 445:
REFERENCES 429 721. Manzoni L, Aros
Page 446 and 447:
REFERENCES 431 762. Baldwin JE, Adl
Page 448 and 449:
REFERENCES 433 808. Leggio A, Liguo
Page 450 and 451:
3 Nitronates SEMA L. IOFFE N. D. Ze
Page 452 and 453:
SYNTHESIS OF NITRONATES 437 as O-nu
Page 454 and 455:
SYNTHESIS OF NITRONATES 439 These r
Page 456 and 457:
SYNTHESIS OF NITRONATES 441 It shou
Page 458 and 459:
X-C(NO 2) 3 NO 2-C(NO 2) 3 R R′ C
Page 460 and 461:
R R′ X NO 2 base −H + R R′ X
Page 462 and 463:
Br NaNO 2/DMF Cl R 6 R=C6H5; CO2MeR
Page 464 and 465:
OH NO 2 R EtO2CN NCO 2Et PPh 3, ben
Page 466 and 467:
NO 2 O Me R 2 R 1 PhSH Et 3N cat. M
Page 468 and 469:
R R O OAc 19 Mn III −H + NO2 Me M
Page 470 and 471:
Ag[ArC(NO2)2] 26 heptane 100°, 50
Page 472 and 473:
NO2CH=C(NO2)Ph [RR′CN 2 28 RR′C
Page 474 and 475:
Me O 2N Me O 2N 29a Br EtO 2CC CCO
Page 476 and 477:
SYNTHESIS OF NITRONATES 461 (39) (s
Page 478 and 479:
SYNTHESIS OF NITRONATES 463 In the
Page 480 and 481:
R 1 R R 2 NO 2 + R 5 R 3 42 43 R 6
Page 482 and 483:
O O N R + R"CO NO2 R′ N 42 43c Ph
Page 484 and 485:
SYNTHESIS OF NITRONATES 469 3.2.2.3
Page 486 and 487:
R R′ C R H C R′ NO2 [RR′C(NO2
Page 488 and 489:
Table 3.1 The silylation of AN by E
Page 490 and 491:
SYNTHESIS OF NITRONATES 475 Table 3
Page 492 and 493:
O Me 2RSi NMe 2 + − Me2N=C—OSiM
Page 494 and 495:
SYNTHESIS OF NITRONATES 479 decompo
Page 496 and 497:
A G N R O N H O O A Si R 1 RR 1 C=N
Page 498 and 499:
NO2CH2CH2CH2CO2ME Me CO2Me NO2CH CH
Page 500 and 501:
SYNTHESIS OF NITRONATES 485 than 20
Page 502 and 503:
R 1 R 2 LDA THF, −78°C R 1 O OLi
Page 504 and 505:
O R 1 N 51o-t OSiMe2R 3 R 2 PRINCIP
Page 506 and 507:
MeO2C H PRINCIPAL PHYSICOCHEMICAL D
Page 508 and 509:
PRINCIPAL PHYSICOCHEMICAL DATA AND
Page 510 and 511:
R' R PRINCIPAL PHYSICOCHEMICAL DATA
Page 512 and 513:
Table 3.8 (continued) PRINCIPAL PHY
Page 514 and 515:
Page 516 and 517:
Page 518 and 519:
Page 520 and 521:
Page 522 and 523:
Page 524 and 525:
Page 526 and 527:
Page 528 and 529:
** NO2 O O N O * N SiMe3 O PRINCIPA
Page 530 and 531:
Page 532 and 533:
XO R 1 N O H XO O N R R 2 = H R 3 X
Page 534 and 535:
EtO 2CCH N(O)OMe Δ or HCl NH3 / Me
Page 536 and 537:
R 1 R 2 OSi N O E—Nu R 1 R 2 REAC
Page 538 and 539:
O OM R′ N 113 R′′ Me 3SiX −
Page 540 and 541:
O O R 1 R 1 N N OSi R 2 OSi R 2 + M
Page 542 and 543:
R 1 PhO2S R 1 PhO 2S N NO2 O OSiMe
Page 544 and 545:
R 3 R 1 O R 4 R 3 R 3 R 1 R 1 55%-7
Page 546 and 547:
RR′C N MeOCO MeO C O OBEt 2 N O O
Page 548 and 549:
REACTIVITY OF NITRONATES 533 Yields
Page 550 and 551:
RO R 4 R 3 R 2 O N R 1 O P(OAlk) 3
Page 552 and 553:
REACTIVITY OF NITRONATES 537 Second
Page 554 and 555:
MeO2C Ph CO2Me O N O X 1 X 2 Ph H R
Page 556 and 557:
R CO2Me TiCl 4 reflux, overnight N
Page 558 and 559:
Me NO2 + Ph Me NO 2 Ph + Bu n O Bu
Page 560 and 561:
R R O2N O2N O N Regioselectivity +
Page 562 and 563:
REACTIVITY OF NITRONATES 547 Ref.33
Page 564 and 565:
REACTIVITY OF NITRONATES 549 Ref.52
Page 566 and 567:
MeO2C MeO 2C 160 N O OMe R OMgBr r.
Page 568 and 569:
R N O N O R N O N O Y Z X xylene, r
Page 570 and 571:
REACTIVITY OF NITRONATES 555 O N O
Page 572 and 573:
RCH2NO2 RHC N RHC N O OH Ac 2O/AcON
Page 574 and 575:
PhCOCH2SCHR′R′′ 180 R′R′
Page 576 and 577:
REACTIVITY OF NITRONATES 561 Both o
Page 578 and 579:
R 185 + R′ 195 NO2 OH ( )n KH; TH
Page 580 and 581:
NaNO2 AcOH 199 200 (+) -citronellen
Page 582 and 583:
O X X X X S 208 D F E SiMe3 NO 2 O
Page 584 and 585:
R′ R′′ HO R O N 213 O ClSi R
Page 586 and 587:
R SiO R AlkO N N R′′ O + R′
Page 588 and 589:
R′ R′ R′ R′ O N OSi 229 OH
Page 590 and 591:
R′′ OH Si - Me2Bu t Si R′ R N
Page 592 and 593:
R = Me R′ = Ph(86%);CO2Me(28%) O
Page 594 and 595:
R′O HO OR′ R′′ R′ O N * *
Page 596 and 597:
REACTIVITY OF NITRONATES 581 orient
Page 598 and 599:
REACTIVITY OF NITRONATES 583 isomer
Page 600 and 601:
O N O 249a-g + R′ 250a,b R O N O
Page 602 and 603:
REACTIVITY OF NITRONATES 587 Experi
Page 604 and 605:
BuO R 1 Me Me Me Et Et Et Me * ** O
Page 606 and 607:
REACTIVITY OF NITRONATES 591 3.4.4.
Page 608 and 609:
N N OH HO H H H HO (−)-hastinecin
Page 610 and 611:
REACTIVITY OF NITRONATES 595 compli
Page 612 and 613:
Four component [4+2] [4+2] [4+2] do
Page 614 and 615:
Bn O O REACTIVITY OF NITRONATES 599
Page 616 and 617:
Me2Si R 1 NO2 R 1 R 2 R 2 291 O EtO
Page 618 and 619:
O 2N R * = EtO + 296 OEt R * OAc Et
Page 620 and 621:
G * OH G * O G * OH: 305 306 OH Ph
Page 622 and 623:
SILYLATION OF NITRO COMPOUNDS AS A
Page 624 and 625:
RCH2CH2CHNO2 319 H a B − BH + SIL
Page 626 and 627:
R 1 R 2 Ph R2 R1 O N OSi NO2 R2 R1
Page 628 and 629:
Page 630 and 631:
Me 2N CH 2 N OSiMe 3 R 1 R 2 + O N
Page 632 and 633:
Ref.459 Ar Ar HF 2 − HF 2 − + N
Page 634 and 635:
R 2 R 3 R 1 NO 2 SiX/Et3N (1) SILYL
Page 636 and 637:
NO 2 NO2 SiX/Et 3N NO 2 Me 3SiCl/DB
Page 638 and 639:
Page 640 and 641:
Page 642 and 643:
C N OH OH C N OH + + OH B Si - trio
Page 644 and 645:
R 2 R3 R4 R 1 O N TfOH O 348f-h R 2
Page 646 and 647:
Page 648 and 649:
R O N OX SILYLATION OF NITRO COMPOU
Page 650 and 651:
Page 652 and 653:
Pheq O N O 356a TfOTBS Pheq O N 357
Page 654 and 655:
(a) SiO O N 6 Nu (b) N N (c) SiO Si
Page 656 and 657:
Page 658 and 659:
Page 660 and 661:
Page 662 and 663:
# N CO2Me OSi OMe SiO N CO2Me OSi S
Page 664 and 665:
Page 666 and 667:
( ) 3 H Ph O N OMe 391a H N Ph O N
Page 668 and 669:
R 2 R 3 R 4 R 2 R 3 R 4 R 2 An O N
Page 670 and 671:
R = CO2Me; NO2;Δ t > 50°C (O 2N)2
Page 672 and 673:
X NO 2 SILYLATION OF NITRO COMPOUND
Page 674 and 675:
Page 676 and 677:
Page 678 and 679:
Page 680 and 681:
Page 682 and 683:
O N An 431(C) OTMS SILYLATION OF NI
Page 684 and 685:
R 1 432 R 1 434 E OR 3 NO2 R 2 N(OS
Page 686 and 687:
X R 1 434 R 2 R 1 432 X + A NO 2 R
Page 688 and 689:
Si - trialkylsilyl N OSi O Si SILYL
Page 690 and 691:
R 1 R 2 441 R 1 R 2 NO2 C NO 2 −
Page 692 and 693:
Page 694 and 695:
R 2 SILYLATION OF NITRO COMPOUNDS A
Page 696 and 697:
Page 698 and 699:
NH 3 N H * + H 2C CO 2Et R 1 = H or
Page 700 and 701:
N N N N R 1 =Me, R 2 =H 92% Bz Me N
Page 702 and 703:
Page 704 and 705:
RN(NO2)SiMe3 RN N + 473a,b OSiMe3 i
Page 706 and 707:
Page 708 and 709:
Cl N OSiMe3 MeO OSiMe3 Me 476d SILY
Page 710 and 711:
R R 495 NO2 493 N(OTBS)2 R′I (Me3
Page 712 and 713:
R 1 N(OSi)2 Nu: (b) R 2 EX (a) Si =
Page 714 and 715:
Page 716 and 717:
Me Me Me Me Me Me Ph eq O 507a Ph N
Page 718 and 719:
Page 720 and 721:
R 3 R 4 R 5 R 3 R 4 R 5 Et3N R 3 R
Page 722 and 723:
R3 R2 R 4 NO2 O R 1 R 1 O N 521 R 2
Page 724 and 725:
X R 2 R 1 NO2 ii For 528a iii For 5
Page 726 and 727:
MeO2C MeO2C MeO2C 528a BSA 530a O N
Page 728 and 729:
Page 730 and 731:
Page 732 and 733:
Page 734 and 735:
Page 736 and 737:
Me 3SiO Me3SiO N Me3SiON Me 3Si H N
Page 738 and 739:
Page 740 and 741:
CONCLUSION 725 those containing fun
Page 742 and 743:
REFERENCES 727 Due to the silylatio
Page 744 and 745:
REFERENCES 729 35. Tartakovsky VA,
Page 746 and 747:
Page 748 and 749:
REFERENCES 733 158. University of I
Page 750 and 751:
REFERENCES 735 221. Kornilov VI, Pa
Page 752 and 753:
REFERENCES 737 273. Shitkin VM, Iof
Page 754 and 755:
REFERENCES 739 329. Harada K, Shimo
Page 756 and 757:
Page 758 and 759:
REFERENCES 743 437. Kim BH, Curran
Page 760 and 761:
REFERENCES 745 491. Ioffe SL, Lyapk
Page 762:
REFERENCES 747 540. Gilchrist TL, R
Page 765 and 766:
750 INDEX 1,3-Dipolar cycloaddition
Page 767 and 768:
752 INDEX Nitrone reactions (contd.
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Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis : Novel ...

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