| 1.Research Institution | Chiba University | |
| 2.Research Area | Physical and Engineering Sciences | |
| 3.Research Field | Advanced Processes | |
| 4.Term of Project | FY1996-FY2000 | |
| 5.Project Number | 96P00304 | |
| 6.Title of Project | Highly Selective Organic Synthesis |
| Name | Institution,Department | Title of Position |
| Tsuneo Imamoto | Faculty of Science, Chiba University | Professor |
8.Core Members
| Names | Institution,Department | Title of Position |
| Katsuyuki Ogura | Faculty of Engineering, Chiba University | Professor |
| Kentaro Yamaguchi | Chemical Analysis Center, Chiba University | Associate Professor |
9.Cooperating Researchers
| Names | Institution,Department | Title of Position |
| Satoru Matsukawa | Faculty of Science, Chiba University | Research Associate |
| Motohiro Akazome | Faculty of Engineering, Chiba University | Lecturer |
| Shouji Matsumoto | Faculty of Engineering, Chiba University | Research Associate |
10.Summary of Research Results
|
Catalytic asymmetric synthesis of useful synthetic intermediates to biologically active compounds has been studied by the use of new P-chirogenic diphosphines as the chiral ligands. Various enamides, α,β-unsaturated phosphonates, and β-dehydroamino acid derivatives were subjected to smooth hydrogenation in the presence of the rhodium complexes to provide the corresponding products with excellent to almost 100% ee. The utility of this procedure was demonstrated by its successful application for the preparation of pharmaceutically important compounds. The reaction mechanism of the asymmetric hydrogenations mentioned above was also studied by multi-nuclear NMR, and the reactive intermediates such as monohydride complexes were observed. A new reaction mechanism accounting for the exceedingly high enantioselectivity has been proposed. Novel organic crystalline compounds exhibiting gold or bronze metal color were discovered during the study directed toward development of new electronic materials. The X-ray structural analyses of these materials indicate that the metallic color is responsible for the electronic interaction of the adjacent molecules in the crystals. The constitution of several Grignard reagents was studied by X-ray crystallography and cold-spray mass spectroscopy. It has been clearly indicated that a complex consisting of alkylmagnesium halide and magnesium halide exists as a major component in the tetrahydrofuran solution. |
11.Key Words
(1)Asymmetric Synthesis、(2)Optically Active Phosphine、(3)Optically Active Amine
(4)Optically Active Phosphonic Acid、(5)Asymmetric Hydrogenation、(6)Functionalized Material
(7)Fluorescent Luminescence、(8)Electroluminescent Device、(9)Grignard Reagent
12.References
| Author | Title of Article | |||
| Matsukawa, Satoru; Okano, Naoko; Imamoto, Tsuneo | Phosphine Catalyzed Aldol Reaction between Ketene Silyl Acetals and Aldehydes: Nucleophilic O-Si and C-Si Bond Cleavage by Phosphines | |||
| Journal | Volume | Year | Pages Concerned | |
| Tetrahedron Lett. | 41 | 2000 | 103 | |
| Author | Title of Article | |||
| Hirakawa, Eiji; Takeda, Nobuhiro; Imamoto, Tsuneo | Synthesis and Properties of New Fused Bicyclic Compounds Containing P-B-S Linkages | |||
| Journal | Volume | Year | Pages Concerned | |
| HeteroCycles | 52 | 2000 | 667 | |
| Author | Title of Article | |||
| Miura, Tomoya; Yamada, Hironari; Kikuchi, Shin-ichi; Imamoto, Tsuneo | Synthesis and Reactions of Optically Active Secondery Dialkylphosphine-Boranes | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Org. Chem. | 65 | 2000 | 1877 | |
| Author | Title of Article | |||
| Ohashi, Atsushi; Matsukawa, Satoru; Imamoto, Tsuneo | Improved Synthesis of 1-Adamantylphosphine and Its Use in the Synthesis of Cyclicphosphines Containing 1-Adamantyl Group | |||
| Journal | Volume | Year | Pages Concerned | |
| HeteroCycles | 52 | 2000 | 905 | |
| Author | Title of Article | |||
| Asakura, Katsuo; Kentaro, Yamaguchi; Imamoto, Tsuneo | Electrospray Ionization Mass Spectrometric Observation of the Coordinative Interaction of α, β-Unsaturated Ketones with Cerium(III) Cation | |||
| Journal | Volume | Year | Pages Concerned | |
| Chem. Lett | 2000 | 424 | ||
| Author | Title of Article | |||
| Ohashi, Atsushi; Imamoto, Tsuneo | 1-tert-Buty1-2-methylphospholane-Borane and its Coupling Product 2, 2'-Bis(1-tert-Butylphospholane-Borane) | |||
| Journal | Volume | Year | Pages Concerned | |
| Acta Cryst. C | 56 | 2000 | 723 | |
| Author | Title of Article | |||
| Matsukawa, Satoru; Imamoto, Tsuneo, | Diphosphine Oxide-Brφnsted Acid Complexes as Novel Hydrogen-Bonded Self-Assembled Molecules | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Am. Chem. Soc. | 122 | 2000 | 12659 | |
| Author | Title of Article | |||
| Imamoto, Tsuneo; Kikuchi, Shin-ichi; Miura, Tomoya; Wada, Yoshiyuki | Stereospecific Reduction of Phosphine Oxides to Phosphines by the Use of a Methylation Reagent and Lithium Aluminum Hydride | |||
| Journal | Volume | Year | Pages Concerned | |
| Org. Lett. | 3 | 2001 | 87 | |
| Author | Title of Article | |||
| Gridnev, Ilya, D.; Yamanoi, Yoshinori; Higashi, Natsuka; Tsuruta, Hideyuki; Yasutake, Masaya; Imamoto, Tsuneo | Asymmetric Hydrogenation Catalyzed by (S, S)-R-BisP*-Rh and (R, R)-R-MiniPHOS Complexes: Scope, Limitation, and Mechanism | |||
| Journal | Volume | Year | Pages Concerned | |
| Advanced Synthesis & Catalysis | 343 | 2001 | 118 | |
| Author | Title of Article | |||
| Imamoto, Tsuneo | New P-Chirogenic Diphosphines and Their Use in Catalytic Asymmetric Reactions | |||
| Journal | Volume | Year | Pages Concerned | |
| Pure Appl. Chem. | in press | |||
| Author | Title of Article | |||
| Gridnev, Ilya, D.; Imamoto, Tsuneo | Reaction of a Rh-MiniPHOS Complex with Dihydrogen: NMR and Computational Study | |||
| Journal | Volume | Year | Pages Concerned | |
| Organometallics | 20 | 2001 | 545 | |
| Author | Title of Article | |||
| Asakura, Katsuo; Imamoto, Tsuneo | Isolation and Structural Characterization of New Samarium(III) Bromide-HMPA Complexes | |||
| Journal | Volume | Year | Pages Concerned | |
| Bull. Chem. Soc. Jpn. | in press | |||
| Author | Title of Article | |||
| Ohashi, Atsushi; Imamoto, Tsuneo | A New Synthetic Route to Unsymmetric P-Chirogenic Bisphosphine Ligands | |||
| Journal | Volume | Year | Pages Concerned | |
| Tetrahedron Lett. | 42 | 2001 | 1099 | |
| Author | Title of Article | |||
| Ohashi, Atsushi; Imamoto, Tsuneo | Highly Enantioselective Hydrogenation of α-Dehydroamino Acids by Rhodium Complexes with New Unsymmetric P-Chirogenic Bisphosphines | |||
| Journal | Volume | Year | Pages Concerned | |
| Org. Lett. | 3 | 2001 | 373 | |
| Author | Title of Article | |||
| Hideyuki, Tsuruta; Imamoto, Tsuneo | P-Chirogenic Monodentate Phosphine Ligands Bearing 2-Biphenyl Group | |||
| Journal | Volume | Year | Pages Concerned | |
| Synlett | in press | |||
| Author | Title of Article | |||
| Hiroyuki Matsui | A Chiral Tweezers-Type Dicarboxylic Acid: Studies on Its Complexation with Amines Utilizing CD Spectrum | |||
| Journal | Volume | Year | Pages Concerned | |
| Bull. Chem. Soc. Jpn. | 73(4) | 2000 | 991-997 | |
| Author | Title of Article | |||
| Ryoji Takahashi | Preparation of Microporous Silica Gel by Sol-Gel Process in the Presence of Ethylene Glycol Oligomers | |||
| Journal | Volume | Year | Pages Concerned | |
| Bull. Chem. Soc. Jpn. | 73(3) | 2000 | 765-774 | |
| Author | Title of Article | |||
| Motohiro Akazome | Synthesis, Solid-State Structures, and Aggregation Motifs of Phosphines and Phosphine Oxides Bearing One 2-Pyridone Ring, | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Org. Chem. | 65(21) | 2000 | 6917-6921 | |
| Author | Title of Article | |||
| Satoshi Sato | Viriations in structure and acidity of silica-alumina during steaming process, | |||
| Journal | Volume | Year | Pages Concerned | |
| Phys. Chem. Chem. Phys. | 3 | 2001 | 885-890 | |
| Author | Title of Article | |||
| Katsuyuki Ogura | Alchemy using organic molecules --Discovery of metal-lustrous crystals | |||
| Journal | Volume | Year | Pages Concerned | |
| Chemistry | 55(5) | 2000 | 40-43 | |
| Author | Title of Article | |||
| Katsuyuki Ogura | Development of organic crystals with metalic luster | |||
| Journal | Volume | Year | Pages Concerned | |
| Chemistry and Chemical Industry | 53(5) | 2000 | 598-601 | |
| Author | Title of Article | |||
| Shoji Matsumoto | New Construction of p-Tolylsulfonyl-Substituted Naphthalenes by Thermal and Photochemical Cyclization of 1-Aryl-4-(methylthio)-2-(p-tolylsulfonyl)-1, 3-butadienes | |||
| Journal | Volume | Year | Pages Concerned | |
| Heteroatom Chemistry | 2001 | in press | ||
| Author | Title of Article | |||
| Mineko Takeda | A New Method for Synthesizing a Pyrrole Ring and Its Application to the Development of New π-systems | |||
| Journal | Volume | Year | Pages Concerned | |
| Heterocycles | 55(2) | 2001 | 231-235 | |
| Author | Title of Article | |||
| Katsuyuki Ogura | A novel method for the construction of a benzene ring: a facile ring-closing reaction of (1E, 3E, 5E)-1-chloro-3-(p-tolylsulfonyl)-1, 3, 5-alkatrienes | |||
| Journal | Volume | Year | Pages Concerned | |
| Tetrahedron Letters | 2001 | in press | ||
| Author | Title of Article | |||
| Motohiro Akazome | Inclusion of Poly(ethylene glycol)s by Crystalline (R)-1-naphthyl)glycyl-(R)-phenylglycine | |||
| Journal | Volume | Year | Pages Concerned | |
| Supramolecular Chemistry | 2001 | in press | ||
| Author | Title of Article | |||
| Ryoji Takahashi | High-Surface-Area Silica with Controlled Pore Size Prepared from Nanocomposite of Silica and Citric Acid | |||
| Journal | Volume | Year | Pages Concerned | |
| J. Phys. Chem. B | 104(51) | 2000 | 12184-12191 | |
| Author | Title of Article | |||
| Satoshi Sato | High-Surface-Area SiO2-ZrO2 Prepared by Depositing Silica on Zirconia n Aqueous Ammonia Solution | |||
| Journal | Volume | Year | Pages Concerned | |
| Journal of Catalysis | 196 | 2000 | 190-194 | |