| Foreword |
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vii | |
| Preface |
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xvii | |
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xix | |
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Asymmetric Synthesis of Epoxides and Aziridines from Aldehydes and Imines |
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1 | (36) |
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Vijayalakshmi A. Moorthie |
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1 | (1) |
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Asymmetric Epoxidation of Carbonyl Compounds |
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1 | (21) |
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Aryl, Vinyl, and Alkyl Epoxides |
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2 | (1) |
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Stoichiometric Ylide-mediated Epoxidation |
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2 | (1) |
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Catalytic Ylide-mediated Epoxidation |
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3 | (5) |
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Discussion of Factors Affecting Diastereo- and Enantioselectivity |
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8 | (2) |
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10 | (1) |
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Epoxy Esters, Amides, Acids, Ketones, and Sulfones |
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11 | (1) |
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Sulfur Ylide-mediated Epoxidation |
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11 | (2) |
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13 | (1) |
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Darzens Reactions in the Presence of Chiral Auxiliaries |
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13 | (5) |
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Darzens Reactions with Chiral Reagents |
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18 | (2) |
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Darzens Reactions with Chiral Catalysts |
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20 | (2) |
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Asymmetric Aziridination of Imines |
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22 | (11) |
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Aziridines Bearing Electron-withdrawing Groups: Esters and Amides |
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23 | (1) |
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23 | (1) |
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Reactions between Imines and Carbenes |
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24 | (3) |
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Aziridines by Guanidinium Ylide Chemistry |
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27 | (1) |
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Aziridines Bearing Alkyl, Aryl, Propargyl, and Vinyl Groups |
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28 | (1) |
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Aryl, Vinyl, and Alkyl Aziridines: Stoichiometric Asymmetric Ylide-mediated Aziridination |
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28 | (3) |
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Aryl, Vinyl, and Alkyl Aziridines: Catalytic Asymmetric Ylide-mediated Aziridination |
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31 | (2) |
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33 | (4) |
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34 | (3) |
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Vinylaziridines in Organic Synthesis |
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37 | (36) |
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37 | (1) |
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Direct Synthesis of Vinylaziridines [1] |
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37 | (10) |
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Addition of Nitrene to Dienes |
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37 | (2) |
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Addition of Allylic Ylides and Related Reagents to Imines |
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39 | (3) |
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Cyclization of Amino Alcohols and Related Compounds |
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42 | (3) |
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Cyclization of Amino Allenes |
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45 | (1) |
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Aziridination of α, β-unsaturated Oximes and Hydrazones |
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46 | (1) |
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Ring-opening Reactions with Nucleophiles |
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47 | (7) |
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47 | (1) |
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Organocopper-mediated Alkylation |
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48 | (3) |
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Reactions with Oxygen Nucleophiles |
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51 | (3) |
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Reactions with Other Nucleophiles |
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54 | (1) |
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Isomerization Including Rearrangement |
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54 | (10) |
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Aza-[3,3]-Claisen Rearrangement |
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55 | (2) |
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57 | (3) |
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Aza-[2,3]-Wittig Rearrangement |
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60 | (2) |
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62 | (1) |
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Rearrangement with an Aryl Group on the Aziridine Carbon |
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62 | (1) |
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63 | (1) |
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64 | (3) |
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Cycloadditions of Isocyanates and Related Compounds |
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64 | (1) |
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Carbonylative Ring-expansion to Lactams |
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65 | (2) |
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Electron Transfer to Vinylaziridines |
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67 | (1) |
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68 | (5) |
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68 | (5) |
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Asymmetric Syntheses with Aziridinecarboxylate and Aziridine-phosphonate Building Blocks |
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73 | (44) |
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73 | (1) |
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Preparation of Aziridine-2-carboxylates and Aziridine-2-phosphonates |
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74 | (13) |
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Preparation of Aziridine-2-carboxylates |
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74 | (1) |
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Cyclization of Hydroxy Amino Esters |
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74 | (2) |
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Cyclization of Hydroxy Azido Esters |
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76 | (1) |
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Cyclization of α-Halo-and α-Sulfonyloxy-β-amino Esters and Amides |
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76 | (1) |
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Aziridination of α, β-unsaturated Esters |
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77 | (2) |
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79 | (3) |
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Aziridination of Aldehydes |
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82 | (1) |
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2-Carboxylation of Aziridines |
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83 | (1) |
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Resolution of Racemic Aziridine-2-carboxylates |
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84 | (1) |
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Preparation of Aziridine-2-phosphonates |
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85 | (2) |
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Reactions of Aziridine-2-carboxylates and Aziridine-2-phosphonates |
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87 | (18) |
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Reactions of Aziridine-2-carboxylates |
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87 | (1) |
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88 | (1) |
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Base-promoted Ring-opening |
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89 | (1) |
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Nucleophilic Ring-opening |
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89 | (8) |
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Electrophilic Substitutions at the C-2 Carbon Atom |
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97 | (1) |
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98 | (4) |
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Conversion to Azirine-2-carboxylates |
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102 | (1) |
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Reactions of Aziridine-2-phosphonates |
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103 | (2) |
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Applications in Natural Product Syntheses |
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105 | (6) |
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111 | (6) |
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112 | (5) |
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117 | (28) |
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117 | (1) |
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Overview and General Features |
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117 | (24) |
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118 | (1) |
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Addition of Nitrenes and Nitrenoids to Alkenes |
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119 | (9) |
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Aziridines by Addition-elimination Processes |
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128 | (1) |
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129 | (1) |
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129 | (3) |
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Aza-Darzens and Analogous Reactions |
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132 | (2) |
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134 | (5) |
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Aziridines through Cyclization |
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139 | (1) |
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139 | (1) |
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From 1,2-Aminoalcohols and 1,2-Aminohalides |
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140 | (1) |
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From 1,2-Azidoalcohols [2, 3] |
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141 | (1) |
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141 | (4) |
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142 | (3) |
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Metalated Epoxides and Aziridines in Synthesis |
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145 | (40) |
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145 | (1) |
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146 | (26) |
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147 | (1) |
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Transannular C--H Insertions in Epoxides of Medium-sized Cycloalkenes |
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147 | (4) |
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Transannular C--H Insertions in Epoxides of Polycyclic Alkenes |
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151 | (1) |
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Nontransannular Examples of C--H Insertion |
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152 | (1) |
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Isomerization of Epoxides to Ketones |
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153 | (2) |
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155 | (2) |
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157 | (6) |
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163 | (1) |
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163 | (1) |
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Silyl-stabilized Lithiated Epoxides |
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164 | (1) |
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Sulfonyl-stabilized Lithiated Epoxides |
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165 | (2) |
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Organyl-stabilized Lithiated Epoxides |
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167 | (3) |
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Remotely Stabilized Lithiated Epoxides |
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170 | (1) |
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Simple Metalated Epoxides |
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171 | (1) |
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172 | (8) |
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173 | (1) |
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Stabilized Metalated Aziridines |
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173 | (2) |
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Nonstabilized Metalated Aziridines |
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175 | (2) |
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177 | (1) |
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178 | (2) |
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180 | (5) |
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180 | (5) |
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Metal-catalyzed Synthesis of Epoxides |
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185 | (44) |
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185 | (1) |
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Oxidants Available for Selective Transition Metal-catalyzed Epoxidation |
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186 | (2) |
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Epoxidations of Olefins Catalyzed by Early Transition Metals |
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188 | (7) |
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Titanium-catalyzed Epoxidations |
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188 | (4) |
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Vanadium-catalyzed Epoxidations |
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192 | (3) |
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Chromium-, Molybdenum-, and Tungsten-catalyzed Epoxidations |
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195 | (6) |
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Homogeneous Systems Using Molybdenum and Tungsten Catalysts and Alkyl Hydroperoxides or Hydrogen Peroxide as the Terminal Oxidant |
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196 | (3) |
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199 | (2) |
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Manganese-catalyzed Epoxidations |
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201 | (7) |
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Hydrogen Peroxide as Terminal Oxidant |
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201 | (3) |
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Manganese-catalyzed Asymmetric Epoxidations |
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204 | (4) |
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Rhenium-catalyzed Epoxidations |
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208 | (11) |
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MTO as Epoxidation Catalyst--Original Findings |
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211 | (1) |
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The Influence of Heterocyclic Additives |
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211 | (3) |
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214 | (1) |
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215 | (2) |
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217 | (1) |
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Asymmetric Epoxidations with MTO |
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218 | (1) |
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Iron-catalyzed Epoxidations |
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219 | (2) |
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Ruthenium-catalyzed Epoxidations |
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221 | (3) |
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224 | (5) |
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225 | (4) |
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Catalytic Asymmetric Epoxide Ring-opening Chemistry |
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229 | (42) |
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229 | (1) |
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Enantioselective Nucleophilic Addition to Meso-Epoxides |
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229 | (21) |
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Nitrogen-centered Nucleophiles |
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229 | (7) |
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Sulfur-centered Nucleophiles |
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236 | (2) |
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Oxygen-centered Nucleophiles |
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238 | (5) |
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Carbon-centered Nucleophiles |
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243 | (4) |
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Halide and Hydride Nucleophiles |
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247 | (3) |
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Kinetic Resolution of Racemic Epoxides |
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250 | (13) |
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Nitrogen-centered Nucleophiles |
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250 | (5) |
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Oxygen-centered Nucleophiles |
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255 | (6) |
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Carbon-centered Nucleophiles |
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261 | (2) |
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Enantioselective Rearrangements of Epoxides |
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263 | (3) |
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266 | (5) |
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266 | (5) |
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Epoxides in Complex Molecule Synthesis |
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271 | (44) |
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271 | (1) |
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Synthesis of Complex Molecules by Intramolecular Ring-opening of Epoxides with Heteronucleophiles |
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271 | (17) |
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Intramolecular C--O Bond-forming Reactions |
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271 | (1) |
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Synthesis of Substituted THF Rings |
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272 | (3) |
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Synthesis of Substituted THP Rings |
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275 | (7) |
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Intramolecular 5-exo and 6-endo Cyclization of Polyepoxides |
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282 | (4) |
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Intramolecular C--N Bond-forming Reactions |
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286 | (2) |
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Synthesis of Complex Molecules by Ring-opening of Epoxides with C-Nucleophiles |
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288 | (11) |
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Intramolecular C--C Bond-forming Reactions |
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288 | (2) |
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Intermolecular C--C Bond-forming Reactions |
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290 | (1) |
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Intermolecular C--C Bond-forming Reactions with Organometallic Reagents |
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290 | (5) |
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Addition Reactions of Metal Enolates of Non-stabilized Esters, Amides, and Ketones to Epoxides |
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295 | (4) |
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299 | (3) |
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Synthesis of Complex Molecules by Rearrangement Reactions of Epoxides |
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302 | (13) |
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309 | (6) |
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Vinylepoxides in Organic Synthesis |
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315 | (34) |
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Synthesis of Vinylepoxides |
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315 | (14) |
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Vinylepoxides from Unfunctionalized Dienes |
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316 | (1) |
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Epoxidation with Dioxiranes |
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316 | (2) |
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Epoxidation with Mn-Salen Catalysts |
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318 | (1) |
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Conversion of Diols into Epoxides |
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319 | (1) |
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Vinylepoxides from Functionalized Dienes |
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320 | (1) |
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From Dienones or Unsaturated Amides |
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320 | (1) |
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321 | (1) |
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Vinylepoxides from Epoxy Alcohols |
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322 | (2) |
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Vinylepoxides from Aldehydes |
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324 | (1) |
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324 | (2) |
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Reaction with Sulfur Ylides |
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326 | (1) |
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Vinylepoxides from Other Substrates |
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327 | (1) |
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327 | (1) |
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Kinetic Resolution of Racemic Epoxides |
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328 | (1) |
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Transformations of Vinylepoxides |
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329 | (14) |
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Intermolecular Opening with Oxygen and Nitrogen Nucleophiles |
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329 | (1) |
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329 | (2) |
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331 | (1) |
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Intramolecular Opening with Oxygen and Nitrogen Nucleophiles |
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332 | (3) |
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Opening with Carbon Nucleophiles |
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335 | (1) |
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335 | (2) |
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337 | (1) |
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338 | (1) |
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338 | (3) |
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341 | (2) |
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343 | (6) |
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343 | (6) |
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The Biosynthesis of Epoxides |
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349 | (50) |
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349 | (1) |
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Cytochrome P450 Monooxygenases |
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350 | (18) |
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Mechanism of Cytochrome P450 Monooxygenases |
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350 | (5) |
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355 | (7) |
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362 | (2) |
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364 | (3) |
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367 | (1) |
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Flavin-dependent Epoxidases |
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368 | (8) |
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368 | (5) |
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373 | (3) |
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376 | (7) |
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Epoxidation through Dehydrogenation |
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383 | (6) |
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383 | (4) |
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387 | (2) |
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389 | (5) |
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394 | (5) |
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394 | (5) |
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Aziridine Natural Products--Discovery, Biological Activity and Biosynthesis |
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399 | (44) |
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Introduction and Overview |
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399 | (1) |
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Mitomycins and Related Natural Products |
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400 | (14) |
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Discovery and Anticancer Properties |
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400 | (1) |
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401 | (5) |
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406 | (8) |
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414 | (14) |
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Discovery and Anticancer Properties |
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414 | (1) |
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415 | (8) |
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423 | (5) |
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Other Aziridine Natural Products |
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428 | (15) |
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428 | (1) |
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428 | (1) |
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Dicarboxyaziridine and Miraziridine A |
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429 | (1) |
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430 | (1) |
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430 | (3) |
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433 | (1) |
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Aziridine Metabolites from Amino Alcohols |
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434 | (1) |
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Azirine and Diazirine Natural Products |
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435 | (2) |
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437 | (6) |
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Epoxides and Aziridines in Click Chemistry |
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443 | (36) |
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443 | (4) |
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Epoxides in Click Chemistry |
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447 | (8) |
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447 | (4) |
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Nucleophilic Opening of Epoxides |
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451 | (4) |
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Aziridines in Click Chemistry |
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455 | (15) |
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455 | (1) |
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Bromine-catalyzed Aziridination of Olefins with Chloramines |
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455 | (4) |
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Aminohydroxylation followed by Cyclodehydration |
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459 | (8) |
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Nucleophilic Opening of Aziridines |
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467 | (3) |
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Aziridinium Ions in Click Chemistry |
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470 | (9) |
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Generation of Aziridinium Ions |
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470 | (1) |
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Nucleophilic Opening of Aziridinium Ions |
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471 | (1) |
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Synthesis of Diamino Esters and β-Lactams |
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472 | (1) |
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Synthesis of Pyrazolo[1,2-α]pyrazoles |
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473 | (2) |
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475 | (4) |
| Index |
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479 | |