| Project/Area Number |
11470465
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Chemical pharmacy
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| Research Institution | HOKKAIDO UNIVERSITY |
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Principal Investigator |
HASHIMOTO Shunichi Hokkaido Univ., Grad. School of Pharm. Sci., Prof., 大学院・薬学研究科, 教授 (80107391)
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| Co-Investigator(Kenkyū-buntansha) |
NAKAMURA Seiichi Hokkaido Univ., Grad. School of Pharm. Sci., Res. Assoc., 大学院・薬学研究科, 助手 (90261320)
NAKAJMA Makoto Hokkaido Univ., Grad. School of Pharm. Sci., Assoc. Prof., 大学院・薬学研究科, 助教授 (50207792)
北垣 伸治 北海道大学, 大学院・薬学研究科, 助手 (20281818)
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| Project Period (FY) |
1999 – 2001
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥14,200,000 (Direct Cost: ¥14,200,000)
Fiscal Year 2001: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2000: ¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 1999: ¥6,600,000 (Direct Cost: ¥6,600,000)
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| Keywords | Ligand / Catalyst / Bisphosphite / Bisoxazoline / N-Oxide / スピロ化合物 / ホスファイト / C-H挿入反応 / アミンN-オキシド / スビロ化合物 |
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| Research Abstract |
The rational design and synthesis of novel chiral ligands directed toward catalytic asymmetric reactionsis currently the focus of attention in synthetic organic chemistry. We have synthesized novel chiral compounds including spirobiindanbisphosphites, bisoxazolines, and N-oxides, which were utilized in several enantioselective reactions as chiral ligands. The results we have obtained are as follows; (1) A highly efficient one-pot construction of optically active 1,1'-spirobiindan-3,3'-dione derivatives has been achieved by exploiting double intramolecular C-H insertion reaction of bisdiazo compounds catalyzed by chiral rhodium(II) complex. The spirobiindandione was easily converted to spirobiindanbisphosphite, which was found to be an efficient chiral ligand for palladium-catalyzed allylic alkylation and rhodium-catalyzed Pauson-Khand reaction. (2) Novel bisoxazoline ligands prepared via rhodium-catalyzed enantioselective C-H insertion reaction have proven to be an efficient chiral ligand for copper-catalyzed Diels-Alder reaction and cyclopropanation. (3) Tandem intramolecular generation and rearrangement of allylic oxomium or sulfonium ylides from diazoesters has been effected with the aid of chiral rhodium(H) complex. (4) A novel method of enantioselective conjugate additions of thiols produced sulfides employing a cadmium complexes of chiral bipyridine N,N'-dioxide as a catalyst. (5) An enantioselective Michael addition of β-keto esters to methyl vinyl ketone employing a chiral N,N'-dioxide-scandium complex as a catalyst afforded the a Michael adduct with good enantioselectivity. (6) Chiral N,N'-dioxides catalyzed enantioselective ring opening of meso-epoxides with silicon tetrachloride to produce optically active chlorohydrins.
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