Summary of Research Project Results Under the JSPS FY2000
"Research for the future Program"



1.Research Institution Kyoto University
 
2.Research Area Physical and Engineering Science
 
3.Research Field Advanced Processes
 
4.Term of Project FY1996-FY2000
 
5.Project Number 96P00302
 
6.Title of Project Future Asymmetric Reaction Process

7.Projetct Leader
Name Institution,Department Title of Position
Hayashi, Tamio Kyoto University, Graduate School of Science Professor

8.Core Members

Names Institution,Department Title of Position
Tomioka, Kiyoshi Kyoto University, Graduate School of Phermaceutical Sciences Professor
Iida, Akira Kyoto University, Graduate School of Phermaceutical Sciences Associate Professor
Uozumi, Yasuhiro Kyoto University, Graduate School of Science Lecturer

9.Cooperating Researchers

10.Summary of Research Results

Catalytic asymmetric synthesis provides an efficient method for the preparation of optically active compounds, because it requires only a catalytic amount of chiral reagents. In our "Future Asymmetric Reaction Process", we have focused our efforts on the asymmetric carbon-carbon bond forming reactions and have succeeded in developing new asymmetric carbon-carbon bond forming reactions which are shown below: 1) Rhodium-catalyzed asymmetric 1,4-addition. 2) Asymmetric synthesis of diarylmethylamines by rhodium-catalyzed asymmetric arylation of imines. 3) Asymmetric synthesis of axially chiral allenes by palladium-catalyzed asymmetric allylic alkylation. 4) Palladium-catalyzed asymmetric cross-coupling. 5) Asymmetric conjugate addition of organolithium reagents in the presence of chiral aminoether or diether ligand. 6) Asymmetric addition of lithium enolates to imines. 7) Asymmetric Michael addition of thiols.

11.Key Words

(1)asymmetric synthesis、(2)catalyst、(3)optically active compound
(4)rhodium、(5)palladium、(6)enolate
(7)phosphine ligand、(8)diether ligand、(9)aminoether ligand

12.References

[Reference Articles]
Author Title of Article
Tamio Hayashi Retention of Regiochemistry of Allylic Esters in Palladium-Catalyzed Allylic Alkylation in the Presence of a MOP Ligand
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 120 1998 1681-1687

Author Title of Article
Tamio Hayashi Rhodium-Catalyzed Asymmetric 1, 4-Addition to 1-Alkenylphosphonates
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 121 1999 11591-11592

Author Title of Article
Tamio Hayashi Rhodium-Catalyzed Asymmetric Arylation of Imines with Organostannanes. Asymmetric Synthesis of Diarylmethylamines
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 122 2000 976-977

Author Title of Article
Tamio Hayashi Chiral Monodentate Phosphine Ligand MOP for Transition-Metal-Catalyzed Asymmetric Reactions
Journal Volume Year Pages Concerned
Acc. Chem. Res. 33 2000 354-362

Author Title of Article
Tamio Hayashi Rhodium-Catalyzed Asymmetric Conjugate Addition of Organoboronic Acids to Nitroalkenes
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 122 2000 10716-10717

Author Title of Article
Masamichi Ogasawara Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral Allenes: A Synergistic Effect of Dibenzalacetone on High Enantioselectivity
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 123 2001 2089-2090

Author Title of Article
Hiroki Fujieda A Temary Complex-Reagent for an Asymmetric Reaction of Lithium Ester Enolates with Imines
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 119 1997 2060-2061

Author Title of Article
Katsumi Nishimura Steric Tuning of Reactivity and Enantioselectivity in Addition of Thiophenol to α, β-Unsaturated Esters Mediated by a Chiral Ligand
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 119 1997 12974-12975

Author Title of Article
Masashi Mizuno The Asymmetric Horner-Wadsworth-Emmons Reaction Mediated by an External Chiral Ligand
Journal Volume Year Pages Concerned
Angew. Chem. Int. Ed. Engl. 37 1998 515-517

Author Title of Article
Takeshi Kambara Formal Asymmetric Synthesis of Cholesterol Absorption Inhibitor Bearing 2-Azaspiro[3.5]nonan-1-one Moiety
Journal Volume Year Pages Concerned
J. Org. Chem. 64 1999 9282-9285

Author Title of Article
Hidetaka Fujihara Copper-Amidophosphine Catalyst in Asymmetric Addition of Organozinc to Imines
Journal Volume Year Pages Concerned
J. Am. Chem. Soc. 122 2000 12055-12056

Author Title of Article
Katsumi Nishimura Catalytic Enantioselective Protonation of Lithium Ester Enolates Generated by Conjugate Addition of Arylthiolate to Enoates
Journal Volume Year Pages Concerned
Angew. Chemie Int. Engl. 40 2001 440-442

[Reference Books]
Author Title of Book
Tamio Hayashi Asymmetric Synthesis. Graphical Abstracts and Experimental Methods
Publisher Year Pages
Kodansha 1998 396

Author Title of Book
Tamio Hayashi Comprehensive Asymmetric Catalysis; pp 319-333; 351-364; 887-907
Publisher Year Pages
Springer 1999 1479

Author Title of Book
Kiyoshi Tomioka Comprehensive Asymmetric Catalysis; pp 1105-1142
Publisher Year Pages
Springer 1999 1479

Author Title of Book
Kiyoshi Tomioka Modern Carbonyl Chemistry; pp 491-505
Publisher Year Pages
Wiley 2000 603


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