| 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 |
| 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
| 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 | |
| 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 | |