THE DIELS-ALDER REACTION
1 DIELS-ALDER REACTION: GENERAL REMARKS 1 1 1 INTRODUCTION 1 1 2 DIENE AND DIENOPHILE 3 1 3 PERICYCLIC DIELS-ALDER REACTION 4 1 4 IONIC AND RADICAL DIELS-ALDER REACTIONS 5 1 5 REGIOCHEMISTRY 10 1 6 STEREOCHEMISTRY 12 15 1 7 RETRO DIELS-ALDER REACTION 18 1 8 HOMO-DIELS-ALDER REACTION 20 1 9 MULTIPLE DIELS-ALDER REACTION 22 1 10 THEORY 1 10 1 REACTIVITY AND SUBSTITUENT EFFECTS 22 1 10 2 REGIOSELECTIVITY 23 1 10 3 STEREOSELECTIVITY 24 REFERENCES 25 2 THERMAL DIELS-ALDER REACTION 29 2 1 INTRODUCTION 29 2 2 CARBON DIELS-ALDER REACTIONS 29 29 2 2 1 OPEN-CHAIN DIENES 37 2 2 2 CYCLOPENTADIENES AND CYCLOHEXADIENES 40 2 2 3 HETEROCYCLIC DIENES 43 2 2 4 OUTER-RING DIENES 49 64 2 2 5 INNER-OUTER-RING DIENES 66 2 2 6 ACROSS-RING DIENES 66 2 3 HETERO-DIELS-ALDER REACTIONS 70 2 3 1 HETERODIENES 2 3 2 HETERODIENOPHILES 74 2 4 INTRAMOLECULAR DIELS-ALDER REACTION 83 2 5 OUTLINED DIELS-ALDER REACTIONS 92 REFERENCES 3 LEWIS-ACID CATALYZED DIELS-ALDER REACTION 99 3 1 INTRODUCTION 99 3 2 CARBON DIELS-ALDER REACTION 100 3 2 1 CYCLOADDITIONS OF CYCLOALKENONES 100 3 2 2 HETEROCYCLIC DIENOPHILES 106 3 2 3 RARE EARTH METALS AND SCANDIUM TRIFLATES 108 3 2 4 BULKY LEWIS ACIDS 110 3 2 5 HETEROCYCLIC DIENES 110 3 2 6 SULFINYL GROUP CONTAINING DIENES AND DIENOPHILES 112 3 2 7 TRANSITION METAL-BASED CATALYSTS 114 3 2 8 HETEROGENEOUS CATALYSIS 115 3 2 9 CHIRAL CATALYSTS 116 3 3 HETERO-DIELS-ALDER REACTION 122 3 3 1 NORMAL DIELS-ALDER REACTIONS SYNTHESIS OF PYRONES AND THIOPYRANS 122 3 3 2 INVERSE DIELS-ALDER REACTIONS SYNTHESIS OF PYRANES 123 3 3 3 PYRONES AND TRIAZINES AS DIENES 126 3 4 HOMO-DIELS-ALDER REACTION 126 3 5 CATIONIC DIELS-ALDER REACTION 128 3 6 OUTLINED DIELS-ALDER REACTIONS 130 REFERENCES 138 4 DIELS-ALDER REACTION FACILITATED BY SPECIAL PHYSICAL AND CHEMICAL METHODS 143 4 1 SOLID-PHASE DIELS-ALDER REACTION 143 4 1 1 INORGANIC SOLID-SURFACE PROMOTED DIELS-ALDER REACTION 143 4 1 2 DIELS-ALDER REACTION USING RESIN-ANCHORED REAGENTS 149 4 2 ULTRASOUND-ASSISTED DIELS-ALDER REACTION 154 4 3 MICROWAVE-ASSISTED DIELS-ALDER REACTION 158 4 4 PHOTO-INDUCED DIELS-ALDER REACTION 163 4 5 DIELS-ALDER REACTION IN MOLECULAR CAVITIES 170 4 6 MICÆLLE-PROMOTED DIELS-ALDER REACTION 174 4 6 1 DIELS-ALDER REACTIONS OF SURFACTANT REAGENTS 174 4 6 2 MICELLAR CATALYSIS 176 4 7 BIOCATALYST-PROMOTED DIELS-ALDER REACTION 180 4 7 1 PROTEINS AND ENZYMES CATALYSIS 180 4 7 2 ANTIBODY CATALYSIS 183 4 8 BRØNSTED ACID-CATALYZED DIELS-ALDER REACTION 185 4 9 MISCELLANEOUS DIELS-ALDER REACTIONS 190 4 10 OUTLINED DIELS-ALDER REACTIONS 194 REFERENCES 200 5 HIGH PRESSURE DIELS-ALDER REACTION 205 5 1 INTRODUCTION 205 5 2 OPEN-CHAIN DIENES 208 5 2 1 CYCLOADDITIONS WITH CARBO DIENO PHILES 208 5 2 2 CYCLOADDITIONS WITH HETERODIENOPHILES 213 5 3 OUTER-RING DIENES 217 5 4 INNER-OUTER-RING DIENES 219 5 5 INNER-RING DIENES 223 5 5 1 CYCLOPENTADIENES AND CYCLOHEXADIENES 223 5 5 2 TROPONES AS DIENES 226 5 5 3 FURANS AND THIOPHENES 229 5 5 4 PYRONES AND PYRIDONES 234 5 6 OUTLINED DIELS-ALDER REACTIONS 237 REFERENCES 246 251 6 DIELS-ALDER REACTION IN UNCONVENTIONAL REACTION MEDIA 6 1 DIELS-ALDER REACTION IN AQUEOUS MEDIUM 251 6 1 1 UNCATALYZED DIELS-ALDER REACTION 252 6 1 2 CATALYZED DIELS-ALDER REACTION 261 6 2 DIELS-ALDER REACTION IN NON-AQUEOUS POLAR SYSTEMS 268 6 2 1 LITHIUM PERCHLORATE-DIETHYL ETHER 268 6 2 2 LITHIUM PERCHLORATE-NITROMETHANE 273 6 2 3 LITHIUM TRIFLUOROMETHANESULFONIMIDE IN ACETONE OR DIETHYL ETHER 274 6 2 4 PARA-CHLOROPHENOL AND ETHYLENE GLYCOL 276 6 2 5 IONIC LIQUIDS 278 6 3 DIELS-ALDER REACTION IN MICROEMULSION 280 6 4 DIELS-ALDER REACTION IN SUPERCRITICAL FLUIDS 284 6 4 1 DIELS-ALDER REACTION IN SUPERCRITICAL WATER 285 6 4 2 DIELS-ALDER REACTION IN SUPERCRITICAL CARBON DIOXIDE 286 6 5 OUTLINED DIELS-ALDER REACTIONS 289 REFERENCES 297