7-Endo Selective Friedel-Crafts Cycylization of Vinylepoxides
| Project/Area Number |
15590017
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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 | Kogakuin University (2004-2006)
Hokkaido Pharmaceutical University School of Pharmacy (2003) |
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Principal Investigator |
NAGUMO Shinji Kogakuin University, Applied Chemistry, Associate Professor (40246765)
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| Project Period (FY) |
2003 – 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: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000)
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| Keywords | Friedel-Crafts reaction / vinylepoxide / 7-endo cyclization / hvdro-2-benzazenine / seven-membered carbocycle / seven-membered cyclic amine / stereoselective / montanine / Montanine / 合成研究 / 10員環アミナール / 環拡大反応 / 2-benzazepine / Friedel-Crafts環化 / 2-ベンザゼピン / 分子内フリーデルクラフツ反応 / エステル基 / 立体反転 |
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| Research Abstract |
Nature abounds with compounds containing seven-membered carbocycles as prominent structure features. An intramolecular Friedel-Crafts reaction of epoxide can be applied to the construction of seven-membered carbocycles. Distinct from other functional groups, epoxide has two reacting point. Consequently, regioselectivity is an important issue in this reaction. It should be noted that 7-endo cyclization by intramolecular Friedel-Crafts reaction is generally difficult because 6-exo cyclization proceeds preferentially. Thus author carried out an intramolecular Friedel-Crafts cyclization of vinylepoxide. As a result, endo cyclization has been found to proceed selectively to give seven-membered ring compounds in high yields.
This procedure has also been applied to the stereo- and regioselective construction of a polyfunctional hydro-2-benzazepine and hydro-2-benzazocine. Selection of Lewis acids was found to be important. TMSOTf promotes 7-endo cyclization to give polyfunctional hydro-2-benzazepines in high yields. On the other hand, the treatment of vinylepoxides with BF_3-Et_2O resulted in the selective formation of an aminal products. The aminal formation was also applied to a ring expansion yielding 10-membered cyclic amine derivative.
Furthermore, the synthetic study of montanine, which is alkaloid containing hydrobenzazepine skeleton, was carried out. As a result, its complete skeleton has been successfully constructed.
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Report
(5 results)
Research Products
(14 results)
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[Journal Article] Facile Synthesis of Medium-Sized Cyclic Amines Based on Friedel-Crafts Reaction via Iminium Cation by Use of Acetylene Dicobalt Complex2007
Author(s)
M., Mizukami, H., Saito, T., Higuchi, M., Imai, H., Bando, N., Kawahara, S., Nagumo
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Journal Title
Tetrahedron Letters 48
Pages: 7228-7231
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Novel Construction of Hydro-2benzazepines Based on 7-endo Selective Friedel-Crafts-type Reaction of Vinyloxiranes2007
Author(s)
S., Nagumo, M., Mizukami, K., Wada, T., Miura, H., Bando, N., Kawahara, Y., Hashimoto, M., Miyashita, H., Akita
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Journal Title
Tetrahedron Letters 48
Pages: 8558-85611
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Synthetic Study of Tautomycin. Part 2 : Synthesis of Ichihara's Fragment Based on Regioselective Enzymatic Acetylation of Complex Molecule2006
Author(s)
Y., Ishii, S., Nagumo, T., Arai, M., Akuzawa, N., Kawahara, H., Akita
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Journal Title
Tetrahedron 62
Pages: 716-725
Description
「研究成果報告書概要(欧文)」より
Related Report
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[Journal Article] Synthetic study of tautomycin. Part 2 : Synthesis of Ichihara' s fragment - based on regioselective enzymatic acetylation of complex molecule2006
Author(s)
Ishii, H., Nagumo, S., Arai, T., Akuzawa, M., Kawahara, N., Akita, H.
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Journal Title
Tetrahedron 62
Pages: 716-725
Related Report
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