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Palladium Catalyzed Trimethylenemethane Cycloadditions

Palladium Catalyzed Trimethylenemethane Cycloadditions. Derek Schipper Fagnou Research Group Department of Chemistry University of Ottawa November 15, 2007. Outline. Introduction Mechanistic Discussion Scope Recent Advances Use in Total Synthesis of (±) Marcfortine B Conclusion.

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Palladium Catalyzed Trimethylenemethane Cycloadditions

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  1. Palladium Catalyzed Trimethylenemethane Cycloadditions Derek Schipper Fagnou Research Group Department of Chemistry University of Ottawa November 15, 2007

  2. Outline • Introduction • Mechanistic Discussion • Scope • Recent Advances • Use in Total Synthesis of (±) Marcfortine B • Conclusion

  3. Introduction

  4. Introduction

  5. Cyclopentane Challenges

  6. Trimethylenemethane (TMM)

  7. Mechanism

  8. Stepwise Mechanism

  9. 13C Kinetic Isotope Effect

  10. 13C Kinetic Isotope Effect

  11. 13C Kinetic Isotope Effect

  12. 13C Kinetic Isotope Effect

  13. Mechanism

  14. Isomerization of TMM-Pd Complex

  15. Isomerization of TMM-Pd Complex

  16. High Pressure Affects Regioselectivity

  17. High Pressure Effects Regioselectivity

  18. [3+2] Cycloadditions

  19. The Tin Effect

  20. The Tin Effect

  21. Asymmetric [3+2] Cycloaddition

  22. Asymmetric [3+2] Cycloaddition

  23. Asymmetric [3+2] Imine Cycloaddition

  24. Enantioselective Spirocycle Formation

  25. Enantioselective Spirocycle Formation

  26. Functionalization

  27. Scope

  28. [3+3] TMM Cycloaddition

  29. Addition to Aziridines

  30. [4+3] TMM Cycloaddition

  31. Extension to 4-Carbon Unit

  32. Extension to 4-Carbon Unit

  33. [6+3] TMM Cycloaddition

  34. TMM Cycloaddition in Synthesis

  35. TMM Cycloaddition in Synthesis

  36. (±) Marcfortine B

  37. Retrosynthetic Analysis

  38. Synthesis of (±) Marcfortine B

  39. Mechanism of TMM cycloaddition

  40. Synthesis of (±) Marcfortine B

  41. Synthesis of (±) Marcfortine B

  42. Mechanism of Radical Cyclization

  43. Synthesis of (±) Marcfortine B

  44. Summary • All carbon 1,3-dipole • Exocyclic alkene provides opportunity for further functionalization • Regio, chemo and stereoselective • Efficient route to 5,6,7 and 9 membered rings

  45. Acknowledgments:

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