| Project/Area Number |
07455366
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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 |
Synthetic chemistry
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| Research Institution | OKAYAMA UNIVERSITY OF SCIENCE |
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Principal Investigator |
OTERA Junzo OKAYAMA UNIV.SCI., APPL.CHEM., PROFESSOR, 工学部, 教授 (20131617)
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| Co-Investigator(Kenkyū-buntansha) |
ORITA Hiroaki OKAYAMA UNIV.SCI., APPL.CHEM., ASSISTANT PROFESSOR, 工学部, 助手 (30262033)
SATO Tsuneo KURASHIKIUNIV.OF SCIENCE AND THE ARTS,PROFESSOR (80183383)
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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 |
¥7,200,000 (Direct Cost: ¥7,200,000)
Fiscal Year 1996: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1995: ¥5,200,000 (Direct Cost: ¥5,200,000)
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| Keywords | gamma-sulfenyl alpha-enone / gamma-alkoxy alpha-enone / gamma-siloxy alpha-enone / back-side attack / stereoselectivity / アルファ、ベータ不飽和アルデヒド / 不斉 / カルボニル / 付加 / 還元 / π-電子 |
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| Research Abstract |
The streochemical sense of both gamma-sulfenyl and-alkoxy substrates is consistently interpreted by situating the most electron-donating group orthogonal to the enone face concurrent with the back-side attack of the nucleophiles. Although the back-side attack may possibly be induced simply by the steric bulk of the substituent in the orthogonal position, we rather advance that the stereoelectronic origin is more plausible on the basis of only a small difference between the phenythio and methylthio derivatives as well as the results with alpha-enals. More significantly, the stereochemical outcome with gamma-siloxy alpha-enones is not consistent with the steric argument because the back-side attack should be hampered by the largest siloxy group resulting in the opposite sense of the stereoselectivity if the steric origin is valid. Obviously, the precise picture of the mechanism would be drawn by dealing with transition states, not with the ground states.
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