| Project/Area Number |
17550046
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Gakushuin University |
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Principal Investigator |
AKIYAMA Takahiko Gakushuin University, Faculty of Science, Professor, 理学部, 教授 (60202553)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2005: ¥2,600,000 (Direct Cost: ¥2,600,000)
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| Keywords | Asymmetric Synthesis / Chiral Bronsted Acid / Asymmetric Catalyst / Imine / Cyclization reaction / Nitrogen Containing Compound / 触媒 / 付加環化反応 / リン酸 / aza Diels-Alder反応 / ヒドロホスホニル化反応 / Mannich型反応 / TADDOL / BINOL |
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| Research Abstract |
We already developed and synthesized a chiral phosphoric acid diester starting from (R)-BINOL and demonstrated its catalytic activity as a chiral Bronsted acid. In order to extend the chiral Bronsted acid catalysis, we have studied the enantioselective nucleophilic addition and cycloaddition reaction toward imines.
Nucleophilic addition of diisopropyl phosphite with aldimine was catalyzed by a phosphoric acid diester bearing 3,5-(CF_3)C_6H_2 groups on 3,3'-position to give a-aminophosphonate with high enantioselectivity.
Aza Diels-Alder reaction of electron-rich dienes such as Danishefsky's diene with aldimine proceeded smoothly to give nitrogen-containing 6-membered rings with high to excellent enantioselectivity.
The reverse electron-demand aza Diels-Alder reaction of electron-rich alkene with aza Diene also proceeded smoothly to give tetrahydroquinoline derivatives with excellent enantioselectivity by means of a phosphoric acid diester bearing 9-anthryl group on the 3,3'-positions.
We have found that the phosphoric acid diesters, derived from (R)-BINOL, exhibit excellent catalytic activity as chiral Bransted acid for the nucleophilic reactions and cycloaddition reactions to give nitrogen-containing compounds with good to excellent optical purity.
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