| Project/Area Number |
07640786
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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 |
物質変換
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| Research Institution | OCHANOMIZU UNIVERSITY |
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Principal Investigator |
NAGANO Hajime OCHANOMIZU UNIV., CHEMISTRY,PROFESSOR, 理学部, 教授 (10114919)
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| Project Period (FY) |
1995 – 1996
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| Project Status |
Completed (Fiscal Year 1996)
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| Budget Amount *help |
¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1996: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1995: ¥900,000 (Direct Cost: ¥900,000)
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| Keywords | Radical reaction / Lewis acid / 1,2-Asymmetric induction / Allylation / Deuteration / Lanthanide / Chelation / ランタノイド |
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| Research Abstract |
Stereoselectivity in the radical-mediated allylation of alpha-bromo-beta-silyloxy esters yielding alpha-allyl-beta-silyloxy esters was remarkably affected when the reaction was conducted in the presence of Ln(fod)_3. In the allylation of alpha-bromo-beta-silyloxysuccinate esters affording preferentially syn diastereomers through the chelated trasition states was required stoichiometric amount of the Lewis acid [Eu(fod)_3 or La(fod)_3] to maximize the stereoselectivities, whereas in the reaction of alpha-bromo-beta-silyloxybutanoateesters and alpha-bromo-beta-silyloxy-beta-phenylpropanoate ester the effect induced by the coordination of Eu(fod)_3 to the ester group was catalytic.
Diastereoselectivity in the radical mediated allylation and deuteration reactions of beta-chiral beta-alkoxy-alpha-bromoaldehyde dimethyl acetals and a related alkoxy bromide were remarkably enhanced when the reactions were conducted in the presence of Lewis acid (MgBr_2-OEt_2 for allylation ; MgI_2 for deuteration).
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