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Stereoselective Cyclopropanation Reactions

Stereoselective Cyclopropanation Reactions. Reporter : Xia Zhao Supervisor : Jianbo Wang 2007-12-14. Contents. Introduction Halomethylmetal Mediated Cyclopropanation Reactions (Simmons-Smith Reactions) Michael-Initiated Ring Closure Other Reactions Summary and Outlook Acknowledgement.

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Stereoselective Cyclopropanation Reactions

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  1. Stereoselective Cyclopropanation Reactions Reporter : Xia Zhao Supervisor : Jianbo Wang 2007-12-14

  2. Contents • Introduction • Halomethylmetal Mediated Cyclopropanation Reactions (Simmons-Smith Reactions) • Michael-Initiated Ring Closure • Other Reactions • Summary and Outlook • Acknowledgement

  3. Introduction

  4. Introduction

  5. Introduction

  6. Halomethylmetal Mediated Cyclopropanation Reactions 1. Introduction Emschwiller firstly reported that diiodomethane reacted with zinc to give iodomethylzinc species in 1929. Simmons and Smith found that (IZnCH2I) could be used for the stereospecific conversion of alkenes to cyclopropanes in 1958. Emschwiller, G. Compt. Rend. 1929,188,1555 Simmons, H. E.; Smith, R. D. J. Am. Chem. Soc. 1958, 80, 5323 6

  7. Halomethylmetal Mediated Cyclopropanation Reactions 1. Introduction Simmons-Smith Reagents : Zn/Cu + CH2I2 (1958) Furukawa’s Reagents : Et2Zn + CH2I2 (1:1) (1966) Sawada Reagents : EtZnI + CH2I2 (1969) Denmark Reagent : Et2Zn + XCH2I (1:2) (1991) Shi Yian : Et2Zn + CH2I2 (1:2) + RXH (2004) Yamamoto : R2AlCH2I (1985) Molander : Sm/Hg + CH2I2 (1987)

  8. Halomethylmetal Mediated Cyclopropanation Reactions 2. RelativeDiastereoselection (Cyclic Alkenes) Wang, T.-Z.; Pinard, E.; Paquette, L. A. J. Am. Chem. Soc.1996, 118, 1309 Momose, T.; Nishio, T.; Kirihara, M. Tetrahedron Lett. 1996, 37, 4987 8

  9. Halomethylmetal Mediated Cyclopropanation Reactions 2. RelativeDiastereoselection (Cyclic Alkenes) Mohamadi, F.; Still, W. C. Tetrahedron Lett. 1986, 27, 893 C. Dale Poulter, E. C. Friedrich, S. Winstein J. Am. Chem. Soc. 1969, 91, 6892

  10. Halomethylmetal Mediated Cyclopropanation Reactions 2. RelativeDiastereoselection (Cyclic Alkenes) 10 Johnson, C. R.; Barbachyn, M. R. J. Am. Chem. Soc. 1982,104, 4290

  11. Halomethylmetal Mediated Cyclopropanation Reactions 2. RelativeDiastereoselection (Acyclic Alkenes) Z uniformly good and high syn- selectivity minimization of A(1,3) strain Charette, A. B.; Lebel, H. J. Org. Chem. 1995, 60, 2966

  12. Halomethylmetal Mediated Cyclopropanation Reactions 2. RelativeDiastereoselection (Acyclic Alkenes) Mohr, P. Tetrahedron Lett.1995, 36, 7221

  13. Halomethylmetal Mediated Cyclopropanation Reactions 2. RelativeDiastereoselection (Acyclic Alkenes) Charette, A. B.; Lebel, H. J. Org. Chem. 1995, 60, 2966

  14. Halomethylmetal Mediated Cyclopropanation Reactions 3.Chiral Auxiliaries 14

  15. Halomethylmetal Mediated Cyclopropanation Reactions 3.Chiral Auxiliaries 15

  16. Halomethylmetal Mediated Cyclopropanation Reactions 4. Chiral Ligands the first practical stoichiometric system for the cyclopropanation of allylic alcohol Ukaji, Y.; Nishimura, M.; Fujisawa, T. Chem. Lett. 1992, 61 Ukaji, Y.; Sada, K.; Inomata, K. Chem. Lett. 1993, 1227 16

  17. Halomethylmetal Mediated Cyclopropanation Reactions 4. Chiral Ligands a major breakthrough in this area 17 Charette, A. B.; Juteau, H. J. Am. Chem. Soc. 1994, 116, 2651

  18. Halomethylmetal Mediated Cyclopropanation Reactions 4. Chiral Ligands Takahashi, H.; Yoshioka, M.; Ohno, M.; Kobayashi, S.Tetrahedron Lett. 1992, 33, 2575 Charette, A. B.; Molinaro, C.; Brochu, C. J. Am. Chem. Soc.2001, 123, 12168

  19. Halomethylmetal Mediated Cyclopropanation Reactions 4. Chiral Ligands 19 Lacasse, M.-C.;Poulard, C.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 12440

  20. Halomethylmetal Mediated Cyclopropanation Reactions 4. Chiral Ligands 20 Lacasse, M.-C.;Poulard, C.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 12440

  21. Halomethylmetal Mediated Cyclopropanation Reactions 4. Chiral Ligands Haifeng Du, Jiang Long, Yian Shi Org. Lett. 2006,8,2827

  22. Halomethylmetal Mediated Cyclopropanation Reactions 5. Other Metal Mediated Cyclopropanation reaction Jose M. Concello n, Humberto Rodr guez-Solla, Carmen Simal Org. Lett. 2007,9,2685 Jose M. Concellon et al. Org. Lett. 2007,9,2981

  23. Halomethylmetal Mediated Cyclopropanation Reactions 6. Summary Substances Control Auxiliaries Control Ligands Control

  24. Michael-Initiated Ring Closure 1. Introduction α-halo carbanions heteroatom-derived ylides (S, P, As,Te) alkoxides, thiolates cyanides, enolates, Grignard reagents, hydrides, phosphites,

  25. Michael-Initiated Ring Closure 1. Introduction

  26. Michael-Initiated Ring Closure 2. Relative Diastereoselection steric effects Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1962, 84, 867 Wender, P. A.; Glass, T. E.; Rawlins, D. B. J. Org. Chem. 1996, 61, 7662

  27. Michael-Initiated Ring Closure 2. Relative Diastereoselection Krief, A.; Dumont, W.; Pasau, P.; Lecomte, P. Tetrahedron 1989,45, 3039

  28. Michael-Initiated Ring Closure 2. Relative Diastereoselection Long-Wu Ye, Xiu-Li Sun, Chuan-Ying Li, Yong Tang J. Org. Chem. 2007, 72, 1335

  29. Michael-Initiated Ring Closure 3. Removable Chiral Auxiliaries Mamai, A.; Madalengoitia, J. S. Tetrahedron Lett. 2000, 41, 9009

  30. Michael-Initiated Ring Closure 3. Removable Chiral Auxiliaries Meyers, A. I.; Romine, J. L.; Fleming, S. A. J. Am. Chem. Soc.1988, 110, 7245 Romo, D.;Romine, J. L.; Midura, W.; Meyers, A. I. Tetrahedron 1990, 46, 4951

  31. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Chiral Lithiated Reagents; Chiral enolates; Chiral ylide ;

  32. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Pyne, S. G.; Dong, Z.; Skelton, B. W.; White, A. H. J. Org. Chem.1997, 62, 2337

  33. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Saverio Florio et al.J. Org. Chem. 2005, 70, 5852

  34. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Hanessian, S., Andreotti, D., Gomtsyan. A, J. Am. Chem. Soc.1995, 117, 10393 Shinohara, N.; Haga, J.; Kitazume, T.; Nakamura,S. J. Org. Chem. 1995, 60, 4363

  35. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Aggarwal, V. K. et al. J Chem Soc Perkin Transactions 1,2000, 19, 3267

  36. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Yong Tang et al J. Am. Chem. Soc.2006,128, 9730

  37. Michael-Initiated Ring Closure 4. Chiral Nucleophiles Jun-Cheng Zheng, Wei-Wei Liao, Yong Tang, Xiu-Li Sun, Li-Xin Dai J. Am. Chem. Soc.2005,127,12222

  38. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters The first example of chiral Lewis acid-mediated MIRC with a sulfur ylide. Mamai, A.; Madalengoitia, J. S. Tetrahedron Lett. 2000, 41, 9009 Arai, S.; Nakayama, K.; Hatano, K.-I.; Shioiri, T. J. Org. Chem. 1998,63, 9572

  39. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters Roxanne K. Kunz and David W. C. MacMillan J. Am. Chem. Soc.2005, 127, 3240

  40. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters Hexin Xie, Liansuo Zu, Jian Wang, Wei Wang J. Am. Chem. Soc.2007, 129, 10887

  41. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters Matthew J. Gaunt et al. Angew. Chem. Int. Ed.2004, 43, 4641

  42. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters

  43. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters Matthew J. Gaunt et al. Angew. Chem. Int. Ed.2006, 45, 6024

  44. Michael-Initiated Ring Closure 5. Stoichiometric and Catalytic Promoters

  45. Michael-Initiated Ring Closure 5. Summary Substances Control NucleophilesControl Promoters Control

  46. Other Methods

  47. Other Methods Ying Chen and X. Peter Zhang. J. Org. Chem. 2007, 72, 5931 Ying Chen, Joshua V. Ruppel, X. Peter Zhang J. Am. Chem. Soc.2007, 129, 12074

  48. Other Methods Christina A. Risatti and Richard E.Taylor. Angew. Chem. Int. Ed.2004, 43, 6671 Bruce J. Melancon, Nicholas R. Perl, and Richard E. Taylor Org. Lett. 2007,9,1425

  49. Other Methods David M. et al. J. Am. Chem. Soc.2007, 129, 4456 F. Dean Toste et al.J. Am. Chem. Soc.2005, 127, 18002

  50. Other Methods Pablo Wessig and Olaf Mühling. Angew. Chem. Int. Ed.2001, 40, 6

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