| Preface |
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ix | |
| Introduction |
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xi | |
| Chapter 1 Synthesis of Pyrroles and N-Vinylpyrroles by the Reaction of Ketones (Ketoximes) with Acetylenes |
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1 | (128) |
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1.1 Heterocyclization of Ketoximes with Acetylene |
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1 | (76) |
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1.1.1 Superbase System Alkali Metal Hydroxide-Dimethyl Sulfoxide as the Reaction Catalyst |
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2 | (4) |
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1.1.2 Effects of Base Nature and Concentration |
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6 | (3) |
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9 | (2) |
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11 | (1) |
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1.1.5 One-Pot Synthesis of Pyrroles from Ketones, Hydroxylamine, and Acetylene |
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12 | (4) |
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1.1.6 Effect of Ketoximes Structure on Yields and Ratio of Pyrroles |
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16 | (66) |
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1.1.6.1 Dialkyl- and Alkylcycloalkylketoximes |
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16 | (1) |
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1.1.6.2 Oximes of Cyclic and Heterocyclic Ketones |
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16 | (31) |
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1.1.6.3 Oximes of Terpenoid Ketones and Their Analogs |
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47 | (4) |
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1.1.6.4 Oximes of Ketosteroids |
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51 | (3) |
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1.1.6.5 Oximes of Alkyl Aryl Ketones |
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54 | (4) |
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1.1.6.6 Oximes of Alkyl Hetaryl Pyrroles |
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58 | (6) |
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1.1.6.7 Functionally Substituted Ketoximes |
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64 | (2) |
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1.1.6.8 Oximes of Diketones: Synthesis of Dipyrroles |
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66 | (1) |
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1.1.6.9 Dioximes of 1,2-Diketones |
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67 | (1) |
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1.1.6.10 Dioximes of 1,3-Diketones |
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68 | (3) |
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1.1.6.11 Dioximes of 1,4-Diketones |
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71 | (1) |
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1.1.6.12 Dioximes Separated by Conjugated Systems |
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72 | (5) |
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1.2 Regiospecificity of the Reaction |
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77 | (5) |
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1.3 Substituted Acetylenes in the Reaction with Ketoximes |
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82 | (8) |
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82 | (2) |
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84 | (1) |
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84 | (3) |
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87 | (3) |
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1.4 Vinyl Halides and Dihaloethanes as Synthetic Equivalents of Acetylene |
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90 | (2) |
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1.5 Intermediate Stages and Side Reactions |
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92 | (21) |
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1.5.1 Formation of 0-Vinyl Oximes |
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92 | (9) |
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1.5.2 Formation of 4H-2-Hydroxy-2,3-Dihydropyrroles |
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101 | (1) |
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1.5.3 Formation of 3H-Pyrroles |
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102 | (1) |
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1.5.4 Formation of Pyridines |
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103 | (4) |
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1.5.5 Formation of Acetylenic Alcohols |
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107 | (1) |
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1.5.6 Side Products Formed in Trace Amounts |
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107 | (6) |
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1.6 6-Carbolines from 3-Acylindoles and Acetylene |
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113 | (2) |
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1.7 Reaction of Ketoximes with Acetylene in the Presence of Ketones: One-Pot Assembly of 4-Methylene-3-oxa-1- azabicyclo[ 3.1.0]hexanes |
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115 | (1) |
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1.8 Transformations of Aldoximes in the Systems MOH/DMSO and MOH/DMSO/Acetylene |
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116 | (3) |
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1.9 Mechanism of Pyrrole Synthesis from Ketoximes and Acetylene |
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119 | (10) |
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1.9.1 Oximes as Nucleophiles in the Reaction with Acetylenes: Literature Analysis |
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119 | (4) |
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1.9.2 Possible Mechanisms of Pyrrole Synthesis from Ketoximes and Acetylene |
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123 | (6) |
| Chapter 2 Novel Aspects of NH- and N-Vinylpyrroles Reactivity |
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129 | (210) |
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2.1 Reactions with Participation of the Pyrrole Ring |
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129 | (169) |
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129 | (8) |
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2.1.1.1 Electron Structure of N-Vinylpyrrolium Ions |
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129 | (1) |
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2.1.1.2 Dimerization of Protonated N-Vinylpyrroles |
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130 | (1) |
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2.1.1.3 Peculiarities of N-Vinylpyrroles Protonation with Hydrogen Halides |
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131 | (1) |
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2.1.1.4 Addition of Hydrogen Halides to the Pyrrole Ring |
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132 | (1) |
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2.1.1.5 Protonation of N-Vinylpyrroles with Superacids |
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132 | (3) |
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2.1.1.6 Protonation of Hetarylpyrroles |
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135 | (2) |
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2.1.2 Hydrogenation and Dehydrogenation |
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137 | (5) |
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137 | (2) |
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2.1.2.2 Selective Dehydrogenation of 4,5,6,7-Tetrahydroindole |
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139 | (1) |
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2.1.2.3 Dehydrogenation of 4,5-dihydrobenz[ g]indole |
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139 | (3) |
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2.1.3 Reactions with Electrophilic Alkenes |
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142 | (12) |
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2.1.3.1 Nucleophilic Addition to Vinyl Sulfones |
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142 | (3) |
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2.1.3.2 Reactions with Tetracyanoethylene |
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145 | (9) |
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2.1.4 Reactions with Acetylene |
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154 | (14) |
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154 | (3) |
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2.1.4.2 Reactions with Electrophilic Acetylenes |
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157 | (10) |
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2.1.4.3 Reactions with 1-Alkylthio-2- chloroacetylenes |
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167 | (1) |
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2.1.5 Cross-Coupling of Pyrroles with Haloacetylenes |
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168 | (25) |
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2.1.5.1 Ethynylation of Pyrroles |
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168 | (14) |
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2.1.5.2 Reaction of 2-Ethynylpyrroles with 2,3-Dichloro-5,6-dicyano-1,4- benzoquinone |
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182 | (8) |
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2.1.5.3 Hydroamination of 2-Ethynylpyrroles |
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190 | (3) |
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2.1.6 Reactions with Carbon Disulfide |
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193 | (49) |
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2.1.6.1 Synthesis of Pyrrolecarbodithioates |
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193 | (9) |
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2.1.6.2 Addition of Pyrrolecarbodithioate Anions to the Multiple Bond |
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202 | (3) |
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2.1.6.3 Reactions of S-Alkylpyrrolecarbodithioates |
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205 | (1) |
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2.1.6.4 Synthesis of Pyrrolothiazolidines |
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206 | (1) |
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2.1.6.5 Synthesis of Pyrrolizin-3-One |
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206 | (8) |
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2.1.6.6 Reactions of Functionally Substituted C-Vinylpyrroles with Hydroxide Anion: Synthesis of Stable Enols |
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214 | (10) |
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2.1.6.7 Reactions of Functionalized 2-Vinylpyrroles with Amines |
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224 | (3) |
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2.1.6.8 Synthesis of 5-Amino-3-(pyrrol-2-yl) pyrazoles |
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227 | (9) |
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2.1.6.9 Synthesis of 5(3)-Amino-3(5)-(pyrrol- 2-yl)isoxazoles |
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236 | (6) |
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2.1.7 Alkylation of Pyrroles with Functional Organic Halides |
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242 | (6) |
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2.1.7.1 Alkylation of Pyrroles with Allyl Halides |
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242 | (1) |
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2.1.7.2 Alkylation of Pyrroles with Propargyl Halides |
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243 | (1) |
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2.1.7.3 Allenylation of Pyrroles with 2,3-Dichloro-1-propene |
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243 | (3) |
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2.1.7.4 Allenylation of Pyrroles with 1,2,3-Trichloropropane |
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246 | (1) |
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2.1.7.5 Ethynylation of Pyrroles with 1,2-Dichloroethene |
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247 | (1) |
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2.1.7.6 Ethynylation of Pyrroles with Trichloroethene |
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247 | (1) |
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2.1.7.7 Epoxymethylation of Pyrroles with Epichlorohydrin |
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247 | (1) |
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2.1.8 Formylation of Pyrroles and Reactions of N-Vinylpyrrole-2-carbaldehydes |
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248 | (24) |
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2.1.8.1 Synthesis of N-Vinylpyrrole-2- carbaldehydes |
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248 | (2) |
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2.1.8.2 Reactions of Pyrrole-2-carbaldehydes with Aromatic Di- and Tetraamines |
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250 | (14) |
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2.1.8.3 Reactions of Pyrrole-2-carbaldehydes with Hydroxylamine, Semicarbazide, Thiosemicarbazide, and Aminoguanidine |
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264 | (2) |
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2.1.8.4 Reactions of N-Vinylpyrrole-2- carbaldehydes with L-Lysine |
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266 | (2) |
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2.1.8.5 Three-Component Reaction of N-Vinylpyrrole-2-carbaldehydes with N-Methylimidazole and Cyanophenylacetylene |
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268 | (1) |
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2.1.8.6 Thiylation of N-Vinylpyrrole-2- carbaldehydes |
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269 | (2) |
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2.1.8.7 N-Vinylpyrrole-2-carbaldehydes as Precursors of N-Vinylpyrrole-2-carbonitriles |
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271 | (1) |
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2.1.9 Trifluoroacetylation |
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272 | (11) |
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283 | (9) |
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2.1.11 Assembly of 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacenes |
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292 | (6) |
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2.1.11.1 Via Meso-Aryldipyrromethenes |
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292 | (5) |
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2.1.11.2 Via Meso-CF3-Dipyrromethenes |
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297 | (1) |
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2.2 Reactions with Participation of the Vinyl Group |
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298 | (39) |
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298 | (3) |
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2.2.2 Electrophilic Addition of Alcohols and Phenols |
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301 | (18) |
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319 | (2) |
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321 | (2) |
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2.2.5 Addition of Secondary Phosphines |
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323 | (1) |
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2.2.6 Reactions with Halophosphines |
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324 | (1) |
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2.2.7 Reactions with Phosphorus Pentachloride |
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325 | (3) |
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2.2.8 Catalytic Arylation of the Vinyl Group (Heck Reaction) |
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328 | (1) |
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2.2.9 Metalation of N-Vinylpyrroles and Their Analogs |
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329 | (6) |
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2.2.9.1 Metalation of N-Vinylpyrrole |
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329 | (3) |
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2.2.9.2 Metalation of N-Allenylpyrrole |
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332 | (3) |
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2.2.9.3 Metalation of N-Ethynylpyrrole |
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335 | (1) |
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335 | (2) |
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337 | (2) |
| References |
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339 | (36) |
| Index |
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375 | |