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

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REACTIONS OF NITRILE OXIDES 69 A phosphorylnitrile oxide (Me2CHO)2P(O)CNO reacts with tetracyanoethylene to give the bisadduct 330 (296). Reaction of cyanodinitrochloromethane with 3-nitrobenzonitrile oxide gives 5-chlorodinitromethyl-3-(3-nitrophenyl)-1,2,4oxadiazole 331 (394). O (Me2CHO)2P N O2N O N CN C C NC 330 N O N O N O N C(NO2)2Cl 331 P(OCHMe) 2 A signiÞcant acceleration of 1,3-dipolar cycloaddition of nitriles with nitrile oxides is shown, in the absence of solvent, at microwave irradiation (395). The reactions are Þnished within 2 to 10 min, to give 1,2,4-oxadiazoles in good yields. A new route to 1,2,4-oxadiazoles and their complexes via Pt- and Pd-mediated 1,3-dipolar cycloaddition of nitrile oxides to organonitriles, has been reported. The sequence of the metal-mediated [2 + 3] cycloaddition offers an alternative route for the preparation of oxadiazoles. SigniÞcant activation of the CN group in organonitriles upon their coordination to a Pt(IV) center has been found in the reaction of [PtCl4(RCN)2] (R= Me, Et, CH2Ph) with stable aromatic nitrile oxides, ArCNO (Ar = 2,4,6-R ′ 3C6H2; R ′ = Me, OMe), to give the (1,2,4-oxadiazole)platinum(IV) complexes, PtCl4.HetH (HetH = 3-Ar-5-R-1,2,4-oxadiazole; Ar and R see above). The [2 + 3] cycloaddition has been performed under mild conditions even starting from complexed acetonitrile and propionitrile, which exhibit low reactivity in the free state. The reaction between complexes PtCl4.HetH and one equivalent of Ph3P:CHCO2Me in CH2Cl2 leads to the appropriate Pt(II) complexes PtCl2.HetH; the reduction fails only in the case of PtCl4.HetH (Ar = mesityl, R = Me) because it is insoluble in most common organic solvents. The oxadiazoles formed in the metal-mediated reaction are liberated, almost quantitatively, from their Pt(IV) complexes by reaction of the latter with an excess of pyridine in CHCl3, giving free 1,2,4-oxadiazoles and trans-[PtCl4(pyridine)2] (396). The reactions between stable 2,4,6-trisubstituted benzonitrile oxides ArCNO and trans-[PdCl2(RCN)2] complexes, or RCN (R = Me, Et, CH2CN, NMe2, Ph), in the presence of PdCl2, proceed under mild conditions and give the 1,2,4-oxadiazole trans-complexes of the type 332 in 40% to 85% yields. In CH2Cl2, the reaction between the nitrile oxides and [PdCl2(MeCN)2] furnishes
70 NITRILE OXIDES complexes [PdCl2(ONCAr)2], which are the Þrst representatives of metal compounds in which nitrile oxides act as ligands. The liberation of the heterocyclic species from 332 is successfully performed by substitution reactions either with 1,2-bis(diphenylphosphino)ethane or with an excess amount of Na2S.7H2O in MeOH (397). R Cl Ar N O N Pd N O N Ar Cl 332 R Ar = 2,4,6-Me3C6H2, 2,4,6-(MeO) 3C6H2 R = Me, Et, CH2CN, NMe2, Ph The cycloaddition of nitrile oxides to nitriles, and its Pt(II) and Pt(IV) complexes, trans-[PtCl2(NCMe)2] andtrans-[PtCl4(NCMe)2], was investigated by quantum chemical methods at different levels of theory, using quasi-relativistic pseudopotentials for the platinum atom. The activation of the nitriles ligated to Pt(IV) can be interpreted in terms of both kinetic (activation parameters) and thermodynamic (reaction energies) viewpoints. The higher reactivity of the Pt(IV) complex, when compared with that of the Pt(II) complex, is kinetically controlled. The calculations predict that the Pt(II) complex should be less reactive than free acetonitrile, and that the relative reactivity of the Pt(II) complex is governed mainly by the entropic factor. The cycloaddition of nitrile oxide to nitriles is mainly controlled by the HOMOnitrile oxide-LUMOnitrile type of interaction and occurs via a concerted asynchronous mechanism for both free and bound nitriles rather than via a stepwise mechanism (398). Mesitylphosphaacetylene 2,4,6-Me3C6H2C≡P, (synthesized by AlCl3-initiated elimination of (Me3Si)2O from Me3SiP = C(OSiMe3)C6H2-2,4,6-Me3), undergoes [3 + 2] cycloaddition reactions with nitrile oxides to yield oxaazaphosphole derivatives (399). 1.3.4.4. Intramolecular Cycloaddition Intramolecular nitrile oxide cycloaddition (INOC) is widely used in the synthesis of various compounds, particularly, natural products. This Þeld is reviewed in detail in Chapter 6 of the monograph/Reference 5 and also in Reference 400 limited to nitrile oxides generated from nitroalkenes. Some features of INOC are illustrated in this subsection by new data and those omitted in Reference 5. Reactions with participation of the C=C bond are the most studied of INOCs. Normal products of such reactions are annulated isoxazolines. A synthesis of bicyclic isoxazolines via sequential Michael and intramolecular 1,3-dipolar additions (403) are mentioned as an example. Michael addition of 1-nitroalkadiene, R 1 R 2 C=CH(CH2)nCH=CHNO2 to allylic stannane R 3 R 4 C=C(R 5 )CH2SnR 6 3
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NITRILE OXIDES, NITRONES, AND NITRO
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NITRILE OXIDES, NITRONES, AND NITRO
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CONTENTS Series Foreword vii List o
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LIST OF ABBREVIATIONS AIBN 2,2’-a
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LIST OF ABBREVIATIONS xi RC radical
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2 NITRILE OXIDES + − − + + −
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4 NITRILE OXIDES NaOHa1 R-CH=NOH Na
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6 NITRILE OXIDES ammonium nitrate (
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8 NITRILE OXIDES R O N N R′ N NO
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10 NITRILE OXIDES HON C(NO 2) Me Me
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12 NITRILE OXIDES which rapidly eli
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14 NITRILE OXIDES Dimethyl furoxan-
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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: 68 NITRILE OXIDES N O O N N N R R R
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
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120 NITRILE OXIDES 324. Stajer G, B
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122 NITRILE OXIDES 382. Himo F, Lov
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124 NITRILE OXIDES 445. Yamamoto T,
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126 NITRILE OXIDES 504. D’ Alelio
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2 Nitrones: Novel Strategies in Syn
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SYNTHESIS OF NITRONES 131 Treated w
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R H OH R N R Oxone K2CO3 OH R N O S
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H N H RO R N H N H CO2H OH O OR P O
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R1 − − R N O 1-CH2-NH-R2 2 BF4
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O N+ O − (EtO) 2P XCH2CN (X = Cl,
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Et H3CO H 3CO − O R R N 1 H N H O
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[O] SYNTHESIS OF NITRONES 143 N H N
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(R 1 O)m O 47 ( )n OH + RNHOH (R 1
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R 5 R 6 R 5 R 6 R6 R5 O R 1 R5 R R6
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+ N O − (EtO)2(O)P HO (EtO)2(O)P
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H O − N O 166, 167 AZN O N − +
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AcO OAc OAc O OAc O OAc OAc O OAc O
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SYNTHESIS OF NITRONES 155 Similarly
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O Ph Et 2N R R 1 S CHO N COOEt R =
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SYNTHESIS OF NITRONES 159 In a simi
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SYNTHESIS OF NITRONES 161 (EtO) 2(O
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R 2 R 1 Cl Ph O · Cl Ph N OR Ph N
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R 1 NO2 R 2 PhSeH R 1 (EtO)2(O)PCH2
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HO MeO2C Br "N-exo" O O O MeO2C 105
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R O N H Ar * SeOTF CH 2Cl 2 R O N H
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SYNTHESIS OF NITRONES 171 (where R
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2 PhCH = NONa H 150 N OH + R 1 R 2
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R 2 R 3 H R 1 R 1 R 2 N O + N OH 16
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R 1 R 2 − O + N OOH R 1 R 2 O OMe
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[R1R2C(NO2)] − + M R3 178 175 (R
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R R R R 188 189 NHOH a: R = Me b: R
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STRUCTURE AND SPECTRA OF NITRONES 1
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R R H C N O + H 3C Bu t + C STRUCTU
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I R 1 − O R 2 ( )n − ( )n N O
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Bu t Ph O N OH − + H H H CF 3 Ph
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Bu N t H O + + N N − − ROCCH2 O
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STRUCTURE AND SPECTRA OF NITRONES 1
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ELECTROCHEMICAL PROPERTIES AND EPR-
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R 2 R 1 N O ELECTROCHEMICAL PROPERT
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NITRONE COMPLEXES 203 radiolysis in
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R 2 226a-c R 1 N O + O N − + −
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R 2 R O C N 1 R2 R3 + R 1 , R 2 , R
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OH _ O + N R 1 a: R 1 = Me, b: R 1
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R Me Me Me Me H N H 259 O O 255a-c
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NITRONE REACTIONS 213 2.6.2. Reduct
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N + O − • + ClO 2 N O • H O C
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H O + N DMPO H O N N 228-232 MeOH P
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Ph H3CO H3CO Ph N O 276 N O 281 O
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Ph N O N F • Ph + Ph F Ph R F Ph
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Ph Ph O O + N O − 286 Rl,Et 3B be
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Table 2.9 Electroreductive coupling
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NITRONE REACTIONS 227 This reaction
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295a Br I NaOH, MeOH NaOH, MeOH NaO
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H 3C R H3C N O − + O N CH3 CH 3 C
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H + O N B− − − − H N − BH
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H H X + O N H RLi O N E X = CH2, NC
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NITRONE REACTIONS 237 Nucleophilic
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O BnO Ph Et 2N O BnO H 317 O O HO N
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NH 2 NH 2 Boc N H2N N(OH)Bn Boc N P
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NITRONE REACTIONS 243 EtAlCl2, TiCl
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NITRONE REACTIONS 245 Addition of v
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HO R R R HO N Bn NHBoc NH 2 NHBoc N
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RCHO BocNHOH R 2 + + O N R1 − PhS
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BzlOOC + NH3 Cl i OH BzlO Cl Cl Bzl
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Table 2.12 Addition a of 2-lithiofu
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H 2N O BnO O OH O CO2H H2N O N H OH
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353 b a BnO BnO 354 Bn N CHO OBn b
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Table 2.13 Addition of organolithiu
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R N O Cl 367 −O + N Bu t LDA, THF
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HO HO OH N N • Ph • O OH O HO P
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RO2C N O X • N O • N O N O •
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N O 373 N O a 374, 376, 377 R2 376
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+ N O − HN HO O R1 S R2 R3 + Ph 1
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+ R 1 N R2 O O R 1 N R 2 − R 1 R
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NITRONE REACTIONS 273 Table 2.14 Sy
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+ Ph N O − Bn + O Et 3SiO MeO O H
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O O O N Pri OCOPh R Me Bn CO 2H NHC
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N O OBu t N O THF,−78°C, 1 h OBu
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O O O O 292 O H N −O + Bn O HO N
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NITRONE REACTIONS 283 The reaction
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O − O O BnO O O + O − O − N P
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R 1 R 2 NH 2 COOH Br a: b: c: d: e:
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NITRONE REACTIONS 289 2.6.6.1.11. N
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NITRONE REACTIONS 291 Nucleophilic
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O − O O + NBoc− O NBoc N Bn 1.
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NITRONE APPLICATION IN RADICAL POLY
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REACTIONS OF DIPOLAR 1,3-CYCLOADDIT
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a b c d REACTIONS OF DIPOLAR 1,3-CY
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R REACTIONS OF DIPOLAR 1,3-CYCLOADD
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a REACTIONS OF DIPOLAR 1,3-CYCLOADD
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− REACTIONS OF DIPOLAR 1,3-CYCLOA
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(a) REACTIONS OF DIPOLAR 1,3-CYCLOA
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O HO REACTIONS OF DIPOLAR 1,3-CYCLO
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Bn REACTIONS OF DIPOLAR 1,3-CYCLOAD
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CO 2Me O O REACTIONS OF DIPOLAR 1,3
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H H REACTIONS OF DIPOLAR 1,3-CYCLOA
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Me REACTIONS OF DIPOLAR 1,3-CYCLOAD
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O REACTIONS OF DIPOLAR 1,3-CYCLOADD
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Ph Ph REACTIONS OF DIPOLAR 1,3-CYCL
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− O Me REACTIONS OF DIPOLAR 1,3-C
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Ph REACTIONS OF DIPOLAR 1,3-CYCLOAD
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B C A Closed [5,6] adduct B B KINUG
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KINUGASA REACTION ([2 + 2] CYCLOADD
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O O N N N O R R O O L 1 : N N N 1 m
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R 1 R 1 O + N 774 a-e Δ O N N Ph 1
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783 784 + N O + CH3 − N O Ph CH3
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R 1 NHOH 793 + R 2 CHO 794 Hydroxyl
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REACTIONS WITH CYCLOPROPANES 397 O
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REFERENCES 399 properties and synth
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REFERENCES 401 (d) Mottley C, Mason
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REFERENCES 403 46. Sankuratri N, Ja
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REFERENCES 405 105. Saladino R, Ner
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REFERENCES 407 159. Sridharan V, Mu
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REFERENCES 409 205. Cupone G, De Ni
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REFERENCES 411 259. Balasundaram B,
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REFERENCES 413 310. (a) Cicchi S, M
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REFERENCES 415 (b) Creary X. Acc. C
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REFERENCES 417 410. Dziembowska T,
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REFERENCES 419 459. Bourquet E, Ban
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REFERENCES 421 Papers of 6-th Inter
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REFERENCES 423 573. Ok D, Fisher MH
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REFERENCES 425 636. (a) Jost S, Gim
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REFERENCES 427 690. Haire DL, Janze
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REFERENCES 429 721. Manzoni L, Aros
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REFERENCES 431 762. Baldwin JE, Adl
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REFERENCES 433 808. Leggio A, Liguo
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3 Nitronates SEMA L. IOFFE N. D. Ze
Page 452 and 453:
SYNTHESIS OF NITRONATES 437 as O-nu
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SYNTHESIS OF NITRONATES 439 These r
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SYNTHESIS OF NITRONATES 441 It shou
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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
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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
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** NO2 O O N O * N SiMe3 O PRINCIPA
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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
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RR′C N MeOCO MeO C O OBEt 2 N O O
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REACTIVITY OF NITRONATES 533 Yields
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RO R 4 R 3 R 2 O N R 1 O P(OAlk) 3
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REACTIVITY OF NITRONATES 537 Second
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MeO2C Ph CO2Me O N O X 1 X 2 Ph H R
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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
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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
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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
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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
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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
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REACTIVITY OF NITRONATES 595 compli
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Four component [4+2] [4+2] [4+2] do
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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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