Transcript 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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Introduction
3
Introduction
4
Introduction
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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
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Halomethylmetal Mediated Cyclopropanation
Reactions
1. Introduction
① Simmons-Smith Reagents : Zn/Cu + CH2I2 (1958)
② Furukawa’s Reagents : Et2Zn + CH2I2 (1:1) (1966)
③ Sawada Reagents : EtZnI + CH2I2 (1969)
④ Denmark Reagent : Et2Zn + XCH2I (1:2) (1991)
⑤ Shi Yian : Et2Zn + CH2I2 (1:2) + RXH (2004)
⑥ Yamamoto : R2AlCH2I (1985)
⑦ Molander : Sm/Hg + CH2I2 (1987)
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Halomethylmetal Mediated Cyclopropanation
Reactions
2. Relative Diastereoselection (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
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Halomethylmetal Mediated Cyclopropanation
Reactions
2. Relative Diastereoselection (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
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Halomethylmetal Mediated Cyclopropanation
Reactions
2. Relative Diastereoselection (Cyclic Alkenes)
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Johnson, C. R.; Barbachyn, M. R. J. Am. Chem. Soc. 1982, 104, 4290
Halomethylmetal Mediated Cyclopropanation
Reactions
2. Relative Diastereoselection (Acyclic Alkenes)
Z uniformly good and high
syn- selectivity
minimization of A(1,3) strain
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Charette, A. B.; Lebel, H. J. Org. Chem. 1995, 60, 2966
Halomethylmetal Mediated Cyclopropanation
Reactions
2. Relative Diastereoselection (Acyclic Alkenes)
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Mohr, P. Tetrahedron Lett. 1995, 36, 7221
Halomethylmetal Mediated Cyclopropanation
Reactions
2. Relative Diastereoselection (Acyclic Alkenes)
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Charette, A. B.; Lebel, H. J. Org. Chem. 1995, 60, 2966
Halomethylmetal Mediated Cyclopropanation
Reactions
3.Chiral Auxiliaries
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Halomethylmetal Mediated Cyclopropanation
Reactions
3.Chiral Auxiliaries
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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
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Halomethylmetal Mediated Cyclopropanation
Reactions
4. Chiral Ligands
a major breakthrough in this area
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Charette, A. B.; Juteau, H. J. Am. Chem. Soc. 1994, 116, 2651
Halomethylmetal Mediated Cyclopropanation
Reactions
4. Chiral Ligands
Takahashi, H.; Yoshioka, M.; Ohno, M.; Kobayashi, S.Tetrahedron Lett. 1992, 33, 2575
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Charette, A. B.; Molinaro, C.; Brochu, C. J. Am. Chem. Soc.2001, 123, 12168
Halomethylmetal Mediated Cyclopropanation
Reactions
4. Chiral Ligands
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Lacasse, M.-C.;Poulard, C.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 12440
Halomethylmetal Mediated Cyclopropanation
Reactions
4. Chiral Ligands
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Lacasse, M.-C.;Poulard, C.; Charette, A. B. J. Am. Chem. Soc. 2005, 127, 12440
Halomethylmetal Mediated Cyclopropanation
Reactions
4. Chiral Ligands
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Haifeng Du, Jiang Long, Yian Shi Org. Lett. 2006, 8, 2827
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
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Halomethylmetal Mediated Cyclopropanation
Reactions
6. Summary
Substances Control
Auxiliaries Control
Ligands Control
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Michael-Initiated Ring Closure
1. Introduction
α-halo carbanions
heteroatom-derived ylides
(S, P, As,Te)
alkoxides, thiolates
cyanides, enolates,
Grignard reagents,
hydrides, phosphites,
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Michael-Initiated Ring Closure
1. Introduction
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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
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Michael-Initiated Ring Closure
2. Relative Diastereoselection
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Krief, A.; Dumont, W.; Pasau, P.; Lecomte, P. Tetrahedron 1989, 45, 3039
Michael-Initiated Ring Closure
2. Relative Diastereoselection
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Long-Wu Ye, Xiu-Li Sun, Chuan-Ying Li, Yong Tang J. Org. Chem. 2007, 72, 1335
Michael-Initiated Ring Closure
3. Removable Chiral Auxiliaries
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Mamai, A.; Madalengoitia, J. S. Tetrahedron Lett. 2000, 41, 9009
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
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Michael-Initiated Ring Closure
4. Chiral Nucleophiles
Chiral Lithiated Reagents;
Chiral enolates;
Chiral ylide ;
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Michael-Initiated Ring Closure
4. Chiral Nucleophiles
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Pyne, S. G.; Dong, Z.; Skelton, B. W.; White, A. H. J. Org. Chem.1997, 62, 2337
Michael-Initiated Ring Closure
4. Chiral Nucleophiles
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Saverio Florio et al. J. Org. Chem. 2005, 70, 5852
Michael-Initiated Ring Closure
4. Chiral Nucleophiles
Hanessian, S., Andreotti, D., Gomtsyan. A, J. Am. Chem. Soc.1995, 117, 10393
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Shinohara, N.; Haga, J.; Kitazume, T.; Nakamura,S. J. Org. Chem. 1995, 60, 4363
Michael-Initiated Ring Closure
4. Chiral Nucleophiles
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Aggarwal, V. K. et al. J Chem Soc Perkin Transactions 1,2000, 19, 3267
Michael-Initiated Ring Closure
4. Chiral Nucleophiles
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Yong Tang et al J. Am. Chem. Soc. 2006,128, 9730
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
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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
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Arai, S.; Nakayama, K.; Hatano, K.-I.; Shioiri, T. J. Org. Chem. 1998, 63, 9572
Michael-Initiated Ring Closure
5. Stoichiometric and Catalytic Promoters
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Roxanne K. Kunz and David W. C. MacMillan J. Am. Chem. Soc. 2005, 127, 3240
Michael-Initiated Ring Closure
5. Stoichiometric and Catalytic Promoters
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Hexin Xie, Liansuo Zu, Jian Wang, Wei Wang J. Am. Chem. Soc. 2007, 129, 10887
Michael-Initiated Ring Closure
5. Stoichiometric and Catalytic Promoters
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Matthew J. Gaunt et al. Angew. Chem. Int. Ed. 2004, 43, 4641
Michael-Initiated Ring Closure
5. Stoichiometric and Catalytic Promoters
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Michael-Initiated Ring Closure
5. Stoichiometric and Catalytic Promoters
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Matthew J. Gaunt et al. Angew. Chem. Int. Ed. 2006, 45, 6024
Michael-Initiated Ring Closure
5. Stoichiometric and Catalytic Promoters
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Michael-Initiated Ring Closure
5. Summary
Substances Control
Nucleophiles Control
Promoters Control
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Other Methods
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Other Methods
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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
Other Methods
Christina A. Risatti and Richard E.Taylor. Angew. Chem. Int. Ed. 2004, 43, 6671
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Bruce J. Melancon, Nicholas R. Perl, and Richard E. Taylor Org. Lett. 2007, 9, 1425
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
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Other Methods
Pablo Wessig and Olaf Mühling. Angew. Chem. Int. Ed. 2001, 40, 6
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Summary and Outlook
Simmons-Smith
Mechanism Study
Other reactions
MIRC
Diazo Decomposed
Computational Chemistry
Natural and Unnatural
Molecules
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Acknowledgement
 Professor
Jianbo Wang
Professors in Organic Institute
All the members in our group
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Thanks for Your Attention !