| Project/Area Number |
11672108
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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 | Toyama Prefectural University |
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Principal Investigator |
NAKAJIMA Noriyuki Toyama Prefectural University, Biotechnology Research Center, Associate Professor, 工学部, 助教授 (40188959)
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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 |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2001: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2000: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
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| Keywords | perfluoroimidates / trichloroacetimidate / hydration / perfluoronitriles / 3,3-sigmatropic rearrangement / glycosylation / ring opening reaction of epoxide / liposidomycin / エポキシトリフルオロアセトイミダート / エポキシトリクロロアセトイミダート / 立体化学 / エポキシ開境反応 / 天然物合成 / トリフルオロアセトアミド / トリフルオロアセトイミダート / ルイス酸触媒によるエポキシドの開環反応 / 活性DMSO種 / 脱離基 |
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| Research Abstract |
We designed and synthesized the perfluoro analogues of benzyl-type, allyl, epoxy and glycosyl imidates in order to improve the chemical properties of trichloroacetimidates. Volatile perfluoronitriles were generated from perfluoroamides with an "activated" dimethyl sulfoxide (DMSO) species at -78 ℃. The key step in perfluoroimidate synthesis was envisioned to be the in situ alcohol addition to perfluoronitriles containing electron-withdrawing substituents on the imidate under dehydration conditions in the presence of DBU.
The obtained trifluoroacetimidates were more stable than the trichloro analogue and were easily purified by SiO_2 column chromatography and/or distillation. Obtained MPM- and DMPM- perfluoroimidates could serve as stable protecting reagents for hydroxy functions in place of the trichloroacetimidate with excellent chemical properties and in comparable yields. The 3,3-sigmatropic rearrangement of allylic analogues, acid-catalyzed cyclization of the epoxy analogues and glycosylation of sugar analogues were next studied. Allyl, epoxy and glycosyl trifluoroacetimidates can serve as an exchangeable precursor for the corresponding trichloro analogues.
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