| Project/Area Number |
13440217
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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 |
物質変換
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| Research Institution | The Kitasato Institute (2002-2003)
Tokyo University of Science (2001) |
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Principal Investigator |
MUKAIYAMA Teruaki The Kitasato Institute, Center for Basic Research, Director, 基礎研究所, 部長 (60016003)
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| Co-Investigator(Kenkyū-buntansha) |
MATSUO Jun-ichi The Kitasato Institute, Center for Basic Research, Researcher, 基礎研究所, 研究員 (50328580)
椎名 勇 東京理科大学, 理学部, 講師 (40246690)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥11,100,000 (Direct Cost: ¥11,100,000)
Fiscal Year 2003: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2002: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2001: ¥3,900,000 (Direct Cost: ¥3,900,000)
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| Keywords | thioformimidate / β-selective mannosylation / one-pot sequential glycosylation / O-linked mucin glycosyl amino acid / glycosyl phosphonium salt / glycosyl phosphite / bromo sugar / α-glycoside / β-選択的マンノシル化学反応 / ワンポット連続的グリコシル化 / グリコシルホスフィナイト糖 / α-グリコシド / 糖質化学 / グリコシル化反応 / シアロシド合成 / 糖鎖合成 / 連続的反応 / トリチル塩 / プロトン酸 / チオグリコシド / F1α抗原 / 枝分かれ型糖鎖 |
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| Research Abstract |
Highly p-selective mannnosylations of glycosyl acceptors with an α-mannosyl 6-nitro-2-benzothiazoate donor were carried out smoothly in the presence of a catalytic amount of tetrakis(pentafluorophenyl)boric acid to afford the corresponding disaccharides in good to high yields.
A mild and highly a-selective glycosylation of several glycosyl acceptors was performed with an in situ formed glycosyl donor, benzyl-protected glycosyl methyldiphenylphosphonium iodide, to afford the corresponding α-disaccharides in high yields in CH2Cl2 at room temperature without any assistance of acid promoters.
A convergent total synthesis of F1a antigen, a member of the tumor-associated O-linked mucin glycosyl amino acid, was tried by one-pot sequential glycosylation. Highly a-selective glycosylation of amino acid with thioglycoside was successfully carried out by combining trityl trifluoromethanesulfonate and N-iodosuccinimide which gave glycosyl amino acid in high yield. Next, the glycosylation of thioglycoside with galactosyl phenyl carbonate or fluoride was tried by the promotion of trityl tetrakis(pentafluorophenyl)borate or trifluoromethanesulfonic acid ; protected F1a was afforded in 80 or 89% overall yield, respectively, by the further addition of glycosyl aminoacid and NIS. The desired trisaccharide was obtained in high yield after removal of the protecting groups.
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