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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

Stereoselective Cyclopropanation Reactions

Reporter : Xia Zhao

Supervisor : Jianbo Wang

2007-12-14

contents
Contents
  • Introduction
  • Halomethylmetal Mediated Cyclopropanation Reactions (Simmons-Smith Reactions)
  • Michael-Initiated Ring Closure
  • Other Reactions
  • Summary and Outlook
  • Acknowledgement
slide6

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

slide7

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)

slide8

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

slide9

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

slide10

Halomethylmetal Mediated Cyclopropanation Reactions

2. RelativeDiastereoselection (Cyclic Alkenes)

10

Johnson, C. R.; Barbachyn, M. R. J. Am. Chem. Soc. 1982,104, 4290

slide11

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

slide12

Halomethylmetal Mediated Cyclopropanation Reactions

2. RelativeDiastereoselection (Acyclic Alkenes)

Mohr, P. Tetrahedron Lett.1995, 36, 7221

slide13

Halomethylmetal Mediated Cyclopropanation Reactions

2. RelativeDiastereoselection (Acyclic Alkenes)

Charette, A. B.; Lebel, H. J. Org. Chem. 1995, 60, 2966

slide16

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

slide17

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

slide18

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

slide19

Halomethylmetal Mediated Cyclopropanation Reactions

4. Chiral Ligands

19

Lacasse, M.-C.;Poulard, C.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 12440

slide20

Halomethylmetal Mediated Cyclopropanation Reactions

4. Chiral Ligands

20

Lacasse, M.-C.;Poulard, C.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 12440

slide21

Halomethylmetal Mediated Cyclopropanation Reactions

4. Chiral Ligands

Haifeng Du, Jiang Long, Yian Shi Org. Lett. 2006,8,2827

slide22

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

slide23

Halomethylmetal Mediated Cyclopropanation Reactions

6. Summary

Substances Control

Auxiliaries Control

Ligands Control

slide24

Michael-Initiated Ring Closure

1. Introduction

α-halo carbanions

heteroatom-derived ylides

(S, P, As,Te)

alkoxides, thiolates

cyanides, enolates,

Grignard reagents,

hydrides, phosphites,

slide26

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

slide27

Michael-Initiated Ring Closure

2. Relative Diastereoselection

Krief, A.; Dumont, W.; Pasau, P.; Lecomte, P. Tetrahedron 1989,45, 3039

slide28

Michael-Initiated Ring Closure

2. Relative Diastereoselection

Long-Wu Ye, Xiu-Li Sun, Chuan-Ying Li, Yong Tang J. Org. Chem. 2007, 72, 1335

slide29

Michael-Initiated Ring Closure

3. Removable Chiral Auxiliaries

Mamai, A.; Madalengoitia, J. S. Tetrahedron Lett. 2000, 41, 9009

slide30

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

slide31

Michael-Initiated Ring Closure

4. Chiral Nucleophiles

Chiral Lithiated Reagents;

Chiral enolates;

Chiral ylide ;

slide32

Michael-Initiated Ring Closure

4. Chiral Nucleophiles

Pyne, S. G.; Dong, Z.; Skelton, B. W.; White, A. H. J. Org. Chem.1997, 62, 2337

slide33

Michael-Initiated Ring Closure

4. Chiral Nucleophiles

Saverio Florio et al.J. Org. Chem. 2005, 70, 5852

slide34

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

slide35

Michael-Initiated Ring Closure

4. Chiral Nucleophiles

Aggarwal, V. K. et al. J Chem Soc Perkin Transactions 1,2000, 19, 3267

slide36

Michael-Initiated Ring Closure

4. Chiral Nucleophiles

Yong Tang et al J. Am. Chem. Soc.2006,128, 9730

slide37

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

slide38

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

slide39

Michael-Initiated Ring Closure

5. Stoichiometric and Catalytic Promoters

Roxanne K. Kunz and David W. C. MacMillan J. Am. Chem. Soc.2005, 127, 3240

slide40

Michael-Initiated Ring Closure

5. Stoichiometric and Catalytic Promoters

Hexin Xie, Liansuo Zu, Jian Wang, Wei Wang J. Am. Chem. Soc.2007, 129, 10887

slide41

Michael-Initiated Ring Closure

5. Stoichiometric and Catalytic Promoters

Matthew J. Gaunt et al. Angew. Chem. Int. Ed.2004, 43, 4641

slide42

Michael-Initiated Ring Closure

5. Stoichiometric and Catalytic Promoters

slide43

Michael-Initiated Ring Closure

5. Stoichiometric and Catalytic Promoters

Matthew J. Gaunt et al. Angew. Chem. Int. Ed.2006, 45, 6024

slide44

Michael-Initiated Ring Closure

5. Stoichiometric and Catalytic Promoters

slide45

Michael-Initiated Ring Closure

5. Summary

Substances Control

NucleophilesControl

Promoters Control

slide47

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

slide48

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

slide49

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

slide50

Other Methods

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

slide51

Summary and Outlook

Simmons-Smith

Mechanism Study

Other reactions

MIRC

Diazo Decomposed

Computational Chemistry

Natural and Unnatural Molecules

slide52

Acknowledgement

  • Professor Jianbo Wang
  • Professors in Organic Institute
  • All the members in our group