| Project/Area Number |
11672098
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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 |
Chemical pharmacy
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| Research Institution | CHIBA UNIVERSITY |
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Principal Investigator |
NISHIDA Atsushi CHIBA UNIVERSITY, FACULTY OF PHARMACEUTICAL SCIENCES, ASSOCIATE PROFESSOR, 薬学部, 助教授 (80130029)
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| Co-Investigator(Kenkyū-buntansha) |
NAKAGAWA Masako CHIBA UNIVERSITY, FACULTY OF PHARMACEUTICAL SCIENCES, PROFESSOR, 薬学部, 教授 (40009171)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2000: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1999: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Keywords | 1, 1'-(2, 2'-bisamino) binaphthalene / axial asymmetry / ytterbiumu (III) triflate / asymmetric Diels-Alder reaction / olefin metathesis / macrolactam / imino ene reaction / sarkomycin / 1,1'-(2,2'-ビスアミノ)ビナフタレン / ルイス酸 / マンニッヒ反応 |
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| Research Abstract |
Amide derivatives of 1,1'- (2, 2'-bisamino) binaphthalene were prepared and examined their ability as a chiral ligand for asymmetric synthesis. 1, 1'- (2, 2'-Bisbenzoylamino) binaphthalene (BINAMIDE) complexed with Yb(OTf)_3 in the presence of tertiary amine. The complex catalyzed asymmetric Diels-Alder reaction between crotonyl imide and cyclopentadine with high diastereo-and enantioselectivity (endo/exo=>95 : 5, >95% e.e.). A substituent on the phenyl ring influenced the activity and selectivity. We also found that dryness of Yb(OTf)_3 is important to obtain active catalyst. Catalytic asymmetric formal total synthesis of antibiotics, sarkomycin was accomplished. A key step of the synthesis was catalytic asymmetric Diels-Alder reaction of bromoacryimide and cyclopentadiene using BINAMIDE complex.
The structure of the active catalyst is not clear now. Cyclic derivatives of BINAMIDE were prepared, in which two acyl groups were connected by ring closing metathesis (RCM). Crystallization and X-ray analysis of the rigid catalyst is under investigation.
We also found that Yb(OTf)_3-TMSCl catalyze imino ene reaction of tosylimine and methylstylene to give homoallyl amines.
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