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



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

7.Projetct Leader
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

[Reference Articles]
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


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