2007 Fiscal Year Final Research Report Summary
Innovational Asymmetric Catalysis縲廾ptimization and New Development
| Project/Area Number |
15002003
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| Research Category |
Grant-in-Aid for Specially Promoted Research
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| Allocation Type | Single-year Grants |
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| Review Section |
Science and Engineering
Chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
SHIBASAKI Masakatsu The University of Tokyo, Graduate School of Pharmaceutical Sciences, 教授 (30112767)
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| Co-Investigator(Kenkyū-buntansha) |
KANAI Motomu The University of Tokyo, Graduate School of Pharmaceutical Sciences, Associate Professor (20243264)
MATSUNAGA Shigeki The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assistant Professor (50334339)
KUMAGAI Naoya The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assistant Professor (40431887)
SOHTOME Yoshihiro The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assitant Professor (50431888)
OHSHIMA Takashi The University of Tokyo, Graduate School of Pharmaceutical Sciences, Assitant Professor (10313123)
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| Project Period (FY) |
2003 – 2007
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| Keywords | asymmetric catalyst / chral tetrasubstituted carbon / anti-influenza drug / bifunctional asymmetric catalyst / pharmaceutical synthesis / Mannich reaction / anti-diabetic agent / Strecker reaction |
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| Research Abstract |
We developed a practical catalytic asymmetric Strecker reaction of ketimines using glucose-derived ligands. Directing toward industrial application, we improved the catalyst turnover efficiency in 100 times using an achiral protic additive. Inexpensive HCN can be used as a cyanide source in this reaction. This is the most general and practical catalytic asymmetric Strecker reacton of ketimines to date. In addition, we developed a new efficient synthetic route of the chiral ligand, which allowed us to synthesize both enantiomers of the ligand. The related catalyst can promote highly enantioselective ring-opening reaction of meso-aziridines with TMSN_3. This reaction was a platform for the synthesis of anti-influenza drug, Tamiflu.
Et_2Zn/linked-BINOL catalyst promoted both anti-and syn-selective direct Mannich reaction of hydroxy ketones. Both diastereomers of the products can be synthesized depening on the reaction conditions with up to 99% ee. The catalyst loading was reduced to 0.01 mol %, which is the far lowest catalyst loading in asymmetric Mannich reaction. The same catalyst also promoted aldol reaction and Michael reaction using the minimum amount of the catalyst.
A chiral rare earth metal-amide catalyst was recently developed, and found to be effective in asymmetric animation reactions. This finding led to develop a practical synthetic route of ranirestat, an anti-diabetic agent.
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Research Products
(215 results)
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[Journal Article] Toward a Rational Design of the Assembly Structure of Polymetallic Asymmetric Catalysts : design, Synthesis, and Evaluation of New Chiral Ligands for Catalytic Asymmetric Cyanation Reactions2007
Author(s)
I. Fujimori, T. Mita, K. Maki, M. Shiro, A. Sato, S, Furusho, M. Kanai, M. Shibasaki
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Journal Title
Tetrahedron 63
Pages: 5820-5831
Description
「研究成果報告書概要(和文)」より
Peer Reviewed
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[Journal Article] Assembly State of Catalytic Modules as Chiral Switches in Asymmetric Strecker Amino Acid Synthesis2006
Author(s)
N. Kato, T. Mita, M. Kanai, B. Therrien, M. Kawano, K. Yamaguchi, H. Danjo, Y. Sei, A. Sato, S. Furusho, M. Shibasaki
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Journal Title
JACS 128
Pages: 6768-6769
Description
「研究成果報告書概要(和文)」より
Peer Reviewed
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[Journal Article] Assembly State of Catalytic Modules as Chiral Switches in Asymmetric Strecker Amino Acid Synthesis2006
Author(s)
N. Kato, T. Mita, M. Kanai, B. Therrien, M. Kawano, K. Yamaguchi, H. Danjo, Y. Sei, A. Sato, S. Furusho, M. Shibasaki
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Journal Title
J. Am. Chem. Soc. 128
Pages: 6768-6769
Description
「研究成果報告書概要(欧文)」より
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