Recent developments and applications in enantioselective desymmetrisation
Download
1 / 52

Recent Developments and Applications in Enantioselective Desymmetrisation - PowerPoint PPT Presentation


  • 120 Views
  • Uploaded on

Recent Developments and Applications in Enantioselective Desymmetrisation. Xin Linghu Department of Chemistry University of North Carolina, Chapel Hill. Outline. Introduction Enantioselective Desymmetrisation of Different Functional Groups Cyclic anhydrides Epoxides

loader
I am the owner, or an agent authorized to act on behalf of the owner, of the copyrighted work described.
capcha
Download Presentation

PowerPoint Slideshow about ' Recent Developments and Applications in Enantioselective Desymmetrisation' - ocean-santos


An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.


- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -
Presentation Transcript
Recent developments and applications in enantioselective desymmetrisation

Recent Developments and Applications in Enantioselective Desymmetrisation

Xin Linghu

Department of Chemistry

University of North Carolina, Chapel Hill


Outline
Outline Desymmetrisation

  • Introduction

  • Enantioselective Desymmetrisation

    of Different Functional Groups

  • Cyclic anhydrides

  • Epoxides

  • Aldehydes and Ketones

  • Alkenes

  • Diols

  • Summary

  • Acknowledgement



Enantioselective desymmetrisation in total synthesis
Enantioselective Desymmetrisation Desymmetrisationin Total Synthesis

1987, Schreiber:

1992, Harada:


Enantioselective desymmetrisation of cyclic anhydride previous work
Enantioselective Desymmetrisation of Cyclic Anhydride: Previous Work

1985, Oda:

configuration

1999, Bolm:

1995, Seebach:


Formation of c x bond via anhydrides
Formation of C-X Bond via Anhydrides Previous Work

Chen, Y.; Tian, S.-K.; Deng, L. J. Am. Chem. Soc. 2000, 122, 9542-9543.


Formation of c c bond via anhydrides
Formation of C-C Bond via Anhydrides Previous Work

Bercot, E. A.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 174-175.


Formation of c c bond via anhydrides1
Formation of C-C Bond via Anhydrides Previous Work

Shintani, R.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 1057-1059.


Formation of c c bond via anhydrides2
Formation of C-C Bond via Anhydrides Previous Work

Shintani, R.; Fu, G. C. Angew. Chem. Int. Ed. 2002, 41, 1057-1059.




Enantioselective ring opening catalyzed by planar chiral pyridine n oxides
Enantioselective Ring Opening Catalyzed by Previous WorkPlanar-Chiral Pyridine N-Oxides

Tao, B.; Lo, M. M. C.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 353-354.


Enantioselective ring opening catalyzed by chiral bipyridine n n dioxide derivatives
Enantioselective Ring Opening Catalyzed by Previous WorkChiral Bipyridine N,N’-Dioxide Derivatives

Nakajima, M.; Saito, M.; Uemura, M.; Hashimoto, S. Tetrahedron Lett.2002, 43, 8827-8829.


Asymmetric ring opening with tmscn catalyzed by pybox yb complexes
Asymmetric Ring Opening with TMSCN Catalyzed by (pybox)Yb Complexes

Schaus, S. E.; Jacobsen, E. N. Org. Lett.2000, 2, 1001-1004.


Enantioselective alkylation of vinyloxiranes
Enantioselective Alkylation of Vinyloxiranes Complexes

Bertozzi, F.; Crotti, P.; Macchia, F.; Pineschi, M.; Arnold, A.; Feringa, B. L. Org. Lett.2000, 2, 933-936.


Desymmetrisation by enantioselective deprotonation
Desymmetrisation by Enantioselective Deprotonation Complexes

Hodgson, D. M.; Gibbs, A. R.; Lee, G. P. Tetrahedron1996, 52, 14361-14384.


Enantioselective a deprotonation of epoxides previous work
Enantioselective Complexesa-Deprotonation of Epoxides: Previous Work

1996, Hodgson:

1996, Hodgson:


Enantioselective b deprotonation of epoxides previous work
Enantioselective Complexesb-Deprotonation of Epoxides: Previous Work

1980, Whitesell and

Felman:

1993, Milne and

Murphy:

1998, Andersson:


Enantioselective alkylative double ring opening of epoxides
Enantioselective Alkylative Double Ring Opening of Epoxides Complexes

Hodgson, D. M.; Maxwell, C. R.; Miles, T. J.; Paruch, E.; Stent, M. A. H.; Matthews, I. R.;

Wilson, F. X.; Witherington, J. Angew. Chem. Int. Ed. 2002, 41, 4313-4316.


Enantioselective alkylative double ring opening of epoxides1
Enantioselective Alkylative Double Ring Opening of Epoxides Complexes

Hodgson, D. M.; Maxwell, C. R.; Miles, T. J.; Paruch, E.; Stent, M. A. H.; Matthews, I. R.;

Wilson, F. X.; Witherington, J. Angew. Chem. Int. Ed. 2002, 41, 4313-4316.


A deprotonated epoxides as nucleophiles
a Complexes-Deprotonated Epoxides as Nucleophiles

Hodgson, D. M.; Gras, E. Angew. Chem. Int. Ed. 2002, 41, 2376-2378.


First desymmetrisation of centrosymmetric diepoxide in natural product synthesis
First Desymmetrisation of Centrosymmetric Diepoxide in Natural Product Synthesis

Holland, J. M.; Lewis, M.; Nelson, A. Angew. Chem. Int. Ed. 2001, 40, 4082-4084.


First desymmetrisation of centrosymmetric diepoxide in natural product synthesis1
First Desymmetrisation of Centrosymmetric Diepoxide in Natural Product Synthesis

Holland, J. M.; Lewis, M.; Nelson, A. Angew. Chem. Int. Ed. 2001, 40, 4082-4084.


Enantioselective desymmetrisation of ketones and aldehydes previous work
Enantioselective Desymmetrisation of Ketones and Aldehydes: Previous Work

1984, Hanessian:

1998, Arai and

Shioiri:

1990, Roush:

1998, Takemoto:


Enantioselective desymmetrisation of ketones and aldehydes previous work1
Enantioselective Desymmetrisation of Ketones and Aldehydes: Previous Work

1998, Ward:

1995, Aubé:

1997, Bolm:


Enantioselective baeyer villiger oxidations by transition metal catalysis
Enantioselective Baeyer-Villiger Oxidations by Transition Metal Catalysis

Uchida, T.; Katsuki, T.; Ito, K.; Akashi, S.; Ishii, A.; Kuroda, T. Helv. Chim. Acta 2002, 85, 3078-3089.

Watanabe, A.; Uchida, T.; Ito, K.; Katsuki, T. Tetrahedron Lett. 2002, 43, 4481-4485.


Enantioselective baeyer villiger oxidations by organocatalysis
Enantioselective Baeyer-Villiger Oxidations by Organocatalysis

Murahashi, S.-I.; Ono, S.; Imada, Y. Angew. Chem. Int. Ed. 2002, 41, 2366-2368.


Rhodium catalyzed desymmetrisation of 4 alkynals
Rhodium-Catalyzed OrganocatalysisDesymmetrisation of 4-Alkynals

Tanaka, K.; Fu, G. C. J. Am. Chem. Soc. 2002, 124, 10296-10297.


Enantioselective reduction of 2 alkyl 1 3 diketones
Enantioselective Reduction Organocatalysisof 2-Alkyl-1,3-diketones

Ohtsuka, Y.; Koyasu, K.; Ikeno, T.; Yamada, T. Org. Lett.2001, 3, 2543-2546.


Synthesis of a potential intermediate for pseudomonic acid b
Synthesis of a Potential Intermediate for Pseudomonic Acid B Organocatalysis

Honda, T.; Kimura, N. Org. Lett.2002, 4, 4567-4570.


Enantioselective desymmetrisation of alkenes previous work
Enantioselective Desymmetrisation of Alkenes: Previous Work Organocatalysis

1987, Schreiber:

1996, Landais:

1990, Ito:


Enantioselective desymmetrisation of alkenes previous work1
Enantioselective Desymmetrisation of Alkenes: Previous Work Organocatalysis

1985, Whitesell:

1992, Mikami:

1994, Martin:


Enantioselective desymmetrisation of alkenes previous work2
Enantioselective Desymmetrisation of Alkenes: Previous Work Organocatalysis

1998, Schrock and Hoveyda:


Preparation of cyclic amines through mo catalyzed asymmetric rcm
Preparation of Cyclic Amines Through Mo-Catalyzed Asymmetric RCM

Dolman, S. J.; Sattely, E. S.; Hoveyda, A. H.; Schrock, R. R. J. Am. Chem. Soc. 2002, 124, 6991-6997.


Enantioselective ru catalyzed rcm
Enantioselective Ru-Catalyzed RCM RCM

Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett.2001, 3, 3225-3228.


Enantioselective ru catalyzed rcm1
Enantioselective Ru-Catalyzed RCM RCM

Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett.2001, 3, 3225-3228.


Tandem catalytic asymmetric rom rcm
Tandem Catalytic Asymmetric ROM/RCM RCM

Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc.2000, 122, 1828-1829.


Tandem catalytic asymmetric rom rcm1
Tandem Catalytic Asymmetric ROM/RCM RCM

Weatherhead, G. S.; Ford, J. G.; Alexanian, E. J.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc.2000, 122, 1828-1829.


Desymmetrisation of meso bicyclic hydrazines by enantioselective hydroboration
Desymmetrisation of Meso Bicyclic Hydrazines by Enantioselective Hydroboration

Luna, A. P.; Ceschi, M. A.; Bonin, M.; Micouin, L.; Husson, H. P.; Gougeon, S.; Estenne-Bouhtou,

G.; Marabout, B.; Sevrin, M.; George, P. J. Org. Chem. 2002, 67, 3522-3524.


Desymmetrisation of meso bicyclic hydrazines by enantioselective hydroboration1
Desymmetrisation of Meso Bicyclic Hydrazines by Enantioselective Hydroboration

Luna, A. P.; Ceschi, M. A.; Bonin, M.; Micouin, L.; Husson, H. P.; Gougeon, S.; Estenne-Bouhtou,

G.; Marabout, B.; Sevrin, M.; George, P. J. Org. Chem. 2002, 67, 3522-3524.


Asymmetric synthesis of polyhydroxylated celastraceae sesquiterpene cores
Asymmetric Synthesis of Polyhydroxylated Celastraceae Sesquiterpene Cores

Spivey, A. C.; Woodhead, S. J.; Weston, M.; Andrews, B. I. Angew. Chem. Int. Ed. 2001, 40, 769-771.


Enantioselective desymmetrisation of meso decalin diallylic alcohols by zr based sae
Enantioselective Desymmetrisation of Meso-Decalin Diallylic Alcohols by Zr-Based SAE

Spivey, A. C.; Woodhead, S. J.; Weston, M.; Andrews, B. I. Angew. Chem. Int. Ed. 2001, 40, 769-771.


Enantioselective desymmetrisation of diols previous work
Enantioselective Desymmetrisation of Diols: Previous Work Alcohols by Zr-Based SAE

1998, Oriyama:

1998, Fu:

1996, Trost:


Enantioselective desymmetrisation of diols previous work1
Enantioselective Desymmetrisation of Diols: Previous Work Alcohols by Zr-Based SAE

1997, Fujioka:

1997, Harada:


Pd catalyzed enantioselective oxidation
Pd-Catalyzed Enantioselective Oxidation Alcohols by Zr-Based SAE

Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. J. Am. Chem. Soc. 2001, 123, 7475-7476.


Asymmetric oxidation of meso diols under photo irradiation
Asymmetric Oxidation of Meso-Diols under Photo-Irradiation Alcohols by Zr-Based SAE

Shimizu, H.; Nakata, K.; Katsuki, T. Chem. Lett.2002, 1080-1081.


Enantioselective desymmetrisation of meso cyclic allylic bisdiethylphosphate
Enantioselective Desymmetrisation of Meso Cyclic Allylic Bisdiethylphosphate

Piarulli, U.; Daubos, P.; Claverie, C; Roux, M; Gennari, C. Angew. Chem. Int. Ed. 2003, 42, 234-236.


Pd catalyzed enantioselective ring opening with dialkylzinc
Pd-Catalyzed Enantioselective Ring BisdiethylphosphateOpening with Dialkylzinc

Lautens, M.; Renaud, J.-L.; Hiebert, S. J. Am. Chem. Soc. 2000, 122, 1804-1805.


Rh catalyzed enantioselective ring opening with organoboronic acids
Rh-Catalyzed Enantioselective Ring Opening with Organoboronic Acids

Lautens, M.; Dockendorff, C.; Fagnou, K.; Malicki, A. Org. Lett.2002, 4, 1311-1314.


Desymmetrisation of diols with a dinuclear zinc asymmetric catalyst
Desymmetrisation of Diols with a Dinuclear Zinc Asymmetric Catalyst

Trost, B. M.; Mino, T. J. Am. Chem. Soc. ASAP


Summary
Summary Catalyst

  • Previous works on the enantioselective desymmetrisation have been introduced briefly according to different functional groups

  • Recent developments in the enantioselective desymmetrisation have been surveyed based on different functional groups

  • Recent applications of enantioselective desymmetrisation in natural products synthesis have been shown


Acknowledgement

Acknowledgement Catalyst

Dr. Jeffrey Johnson

Johnson group


ad