Recent Advances on the Preparation and Reactivity of Methylenecyclopropanes

Introduction .......................................................................................210 I. Preparation of MCPs..........................................................................210 1. MCPs without Additional Functional Groups.............................................. 210 2. MCPs with Functional Groups on the C C Bond ....................................... 211 3. MCPs with Functional Groups on the Cyclopropyl Ring .............................. 212 4. Vinylidenecyclopropanes and Alkylidenecyclopropa[b]naphthalenes ............ 212 5. Recently Developed Methods for the Synthesis of MCPs .............................. 213 II. Transition Metal-catalyzed Reactions of MCPs...................................217 1. Palladium-catalyzed Reactions of MCPs ..................................................... 219 2. Nickelor Platinum-catalyzed Reactions of MCPs ....................................... 225 3. Coinage Metal-catalyzed Reactions of MCPs............................................... 228 4. Other Transition Metal-catalyzed Reactions of MCPs .................................. 232 III. Free Radical Reactions of MCPs.........................................................233 1. Reactions With Carbon Free Radicals......................................................... 234 2. Reactions With Phosphorus, Sulfur or Selenium Free Radicals.................... 234 3. Other Examples of MCP Free Radical Reactions......................................... 240 IV. Direct Additions of Electrophiles to MCPs..........................................240 1. Addition of Protons.................................................................................... 240 2. Addition of Halogen Cations ...................................................................... 240 3. Addition of Sulfur or Selenium Cations ...................................................... 242 V. Lewis Acid Catalyzed Reactions of MCPs...........................................243 1. Addition of Protic Nucleophiles .................................................................. 243 2. Cycloadditions........................................................................................... 244 3. Friedel-Crafts Reactions ............................................................................ 245 4. Additions of Acyl Chloride ......................................................................... 248 5. Se Se or S S Bond Cleavage and the Electrophilic Addition to MCPs........ 250 6. Rearrangements ........................................................................................ 251 7. Other Reactions......................................................................................... 251 VI. Other Types of Reactions....................................................................253 Conclusion .........................................................................................253 Acknowledgement ..............................................................................254 References..........................................................................................254