Breakthrough design of unusual transition states in stereoselective glycosylations
| Project/Area Number |
16KT0061
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Multi-year Fund |
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| Section | 特設分野 |
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| Research Field |
Transition State Control
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| Research Institution | Toho University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
山田 英俊 関西学院大学, 理工学部, 教授 (90200732)
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| Project Period (FY) |
2016-07-19 – 2019-03-31
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| Project Status |
Completed (Fiscal Year 2018)
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| Budget Amount *help |
¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000)
Fiscal Year 2018: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000)
Fiscal Year 2017: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2016: ¥7,410,000 (Direct Cost: ¥5,700,000、Indirect Cost: ¥1,710,000)
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| Keywords | グリコシル化反応 / 立体制御 / α-グルコシド / β-マンノシド / 3,6-架橋糖 / 2,6-ラクトン / 立体選択性 / 3,6-位架橋糖 / 立体配座制御 / グリコシルカチオン / 立体配座 / マンノシル化 / 立体選択的反応 / SN2様反応 / 合成化学 / 計算化学 / 糖質化学 / 立体化学制御 |
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| Outline of Final Research Achievements |
We have designed and made use of two classes of glycosyl donors with unusual conformations. 2,6-Lactones are rigidly fixed to a boat-like conformation and offer 1,2-cis-β-stereoselective glycosylations through stereoinvertive mechanisms, whereas 3,6-loosely-bridged glucoses are supple and offer 1,2-cis-α-stereoselective glycosylations via the corresponding glycosyl cations. The latter allowed us to synthesize record-small cyclodextrins, which are composed of three or four sugar residues.
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| Academic Significance and Societal Importance of the Research Achievements |
生体反応では，糖の多様な立体配座を巧みに駆使し，高効率な反応を実現しているのに対し，化学的グリコシル化反応では，38の（準）安定配座のうち，極めて限られた配座のみが用いられてきた．一方，本研究では，従来活用されてこなかった配座に固定された糖（配座固定糖）や，従来よりも容易に配座を転換できる糖（配座柔軟化糖）をデザイン・合成し，それらが，糖質の精密合成において威力を発揮することを示した．
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Report
(4 results)
Research Products
(62 results)
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[Journal Article] xidative Desulfurization of Electron-Donating 5,5,7,7-Tetraaryl-5,7-dihydrodibenzo[c,e]thiepins and the Related Heterocycles: Generation of Dicationic Dyes upon Two-Electron Oxidation2017
Author(s)
T. Suzuki, T. Kuroda, H. Tamaoki, S. Higasa, T. Nehira, R. Katoono, Y. Ishigaki, K. Fujiwara, T. Fukushima, H. Yamada
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Journal Title
Heterocycles
Volume: 95(2),
Issue: 2
Pages: 816-829
DOI
Related Report
Peer Reviewed / Open Access / Acknowledgement Compliant
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