Synthesis of kojitriose using silicon-tethered glycosidation.

Acta chemica Scandinavica (Copenhagen, Denmark : 1989) Pub Date : 1996-10-01 DOI:10.3891/acta.chem.scand.50-0931

M Bols

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引用次数: 0

Abstract

Reaction of 3,4,6-tri-O-acetyl-beta-D-glucopyranosyl chloride (1) with potassium phenylselenate gave phenyl 3,4,6-tri-O-acetyl-1-seleno-alpha, beta-D-glucopyranoside (2) in 59% yield. Silylation of benzyl 3,4,6-tri-O-benzyl-beta-D-glucopyranoside (4) with ethyl 3,4,6-tri-O-benzyl-2-O-chlorodimethylsilyl-1-thio-beta -D-glucopyranoside gave benzyl 2-O-(3,4, 6-tri-O-benzyl-1-S-ethyl-1-thio-beta-D-glucopyranos-2-O-yldimet hylsilyl)-3,4,6,-tri-O-benzyl-beta-D-glucopyranoside (5) in 35% yield. Reaction of 5 with N-iodosuccinimide in nitromethane gave benzyl 2-O-(3,4, 6-tri-O-benzyl-alpha-D-glucopyranosyl)-3,4, 6-tri-O-benzyl-beta-D-glucopyranoside (6) in 45% yield. Chlorodimethylsilylation of phenyl 3,4, 6-tri-O-acetyl-1-seleno-alpha-D-glucopyranoside (2 alpha) and reaction with 6 gave benzyl 2-O-[2-O-(3,4,6 -tri-O-acetyl-1-Se-phenyl-1-seleno-alpha-D-glucopyranos-2-O-yld imethylsilyl) -3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl]-3,4,6-tri-O-benzyl-beta-D- glucopyranoside (7) in 82% yield. Intramolecular glycosidation of 7 using N-iodosuccinimide in nitromethane gave benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-alpha-D-glucopyranosyl)-3, 4,6-tri-O-benzyl-alpha-D-glucopyranosyl]-3, 4,6-tri-O-benzyl-beta-D-glucopyranoside (8) in 45% yield. Deprotection of 8 gave kojitriose (9) in quantitative yield. Chlorodimethylsilylation of 1,3,4,6-tetra-O-benzyl-alpha, beta-D-fructofuranose (10) with dimethyldichlorosilane and pyridine followed by reaction with ethyl 3,4, 6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (3) gave ethyl 2-O-(1,3,4,6-tetra-O-benzyl-alpha, beta-D-fructofuranosyloxydimethylsilyl)-3,4, 6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (11) in 85% yield. Chlorodimethylsilylation of 1,3,4, 6-tetra-O-benzoyl-alpha-D-fructofuranose (12) with dimethyldicholorosilane and triethylamine followed by reaction with phenyl 3,4, 6-tri-O-acetyl-1-thio-alpha-D-glucopyranoside (13) gave phenyl 2-O-(1,3,4, 6-tetra-O-benzoyl-alpha-D-fructofuranosyloxydimethylsilyl)-3, 4,6-tri-O-acetyl-1-thio-alpha-D-glucopyranoside (14) in 62% yield. Both 11 and 14 failed to undergo intramolecular glycosidation.

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硅系糖基化法合成茴香糖。

3,4,6-三- o-乙酰- β - d -葡萄糖吡喃酰氯(1)与苯基硒酸钾反应得到3,4,6-三- o-乙酰-1-硒- β - d -葡萄糖吡喃苷(2)，收率59%。苄基3,4,6-三- o-苄基- β - d -葡萄糖吡喃苷(4)与3,4,6-三- o-苄基-2-O-氯二甲基硅基-1-硫- β - d -葡萄糖吡喃苷乙基硅化反应得到苄基2-O-(3,4,6-三- o-苄基-1- s-乙基-硫- β - d -葡萄糖吡喃苷-2-O-基二甲基硅基)-3,4,6，-三- o-苄基- β - d -葡萄糖吡喃苷(5)，产率为35%。5与n -碘琥珀酰亚胺在硝基甲烷中反应得到2-O-(3,4,6 -三- o -苄基- - d -葡萄糖吡喃基)- 3,4,6 -三- o -苄基- - d -葡萄糖吡喃苷(6)，产率为45%。苯基3,4,6-三- o-乙酰基-1-硒- d -葡萄糖吡喃苷(2 α)经氯二甲基硅化反应，与6反应得到2- o- [2- o-(3,4,6 -三- o-乙酰基-1-硒-1-硒- d -葡萄糖吡喃苷-2- o-基甲基硅基]-3,4,6-三- o-苄基- α - d -葡萄糖吡喃苷]-3,4,6-三- o-苄基- β - d -葡萄糖吡喃苷(7)，产率82%。用n -碘丁二酰亚胺在硝基甲烷中糖化7得到2-O-[2-O-(3,4,6-三- o -乙酰- - d -葡萄糖吡喃基)- 3,4,6-三- o -苄基- - d -葡萄糖吡喃基]- 3,4,6-三- o -苄基- - d -葡萄糖吡喃基(8)，产率为45%。去保护8个得到小檗(9)的定量产量。用二甲基二氯硅烷和吡啶将1,3,4,6-四- o-苄基- α - d -果糖呋喃糖(10)氯二甲基硅化，然后与3,4,6-三- o-苄基-1-硫- β - d -葡萄糖吡喃苷(3)乙基反应，得到2-O-(1,3,4,6-四- o-苄基- α - d -果糖呋喃基氧基二甲基硅基)- 3,4,6-三- o-苄基-1-硫- β - d -葡萄糖吡喃苷(11)，收率为85%。用二甲基二氯氯硅烷和三乙胺对1,3,4,6 -四- o-苯甲酰- α - d -果糖呋喃糖(12)进行氯二甲基硅化反应，然后与苯基3,4,6 -三- o-乙酰-1-硫- d -葡萄糖吡喃糖(13)反应得到苯基2-O-(1,3,4,6 -四- o-苯甲酰- α - d -果糖呋喃氧基二甲基硅基)- 3,4,6 -三- o-乙酰-1-硫- α - d -葡萄糖吡喃糖(14)，产率为62%。11和14均未发生分子内糖苷化。

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Acta chemica Scandinavica (Copenhagen, Denmark : 1989)

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