使用硅连接糖苷化法合成曲三糖
Synthesis of kojitriose using silicon-tethered glycosidation.
作者信息
Bols M
机构信息
Department of Chemistry, Aarhus University, Denmark.
出版信息
Acta Chem Scand (Cph). 1996 Oct;50(10):931-7. doi: 10.3891/acta.chem.scand.50-0931.
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.
3,4,6-三-O-乙酰基-β-D-吡喃葡萄糖基氯（1）与苯亚硒酸钾反应，以59%的产率得到苯基3,4,6-三-O-乙酰基-1-硒代-α,β-D-吡喃葡萄糖苷（2）。苄基3,4,6-三-O-苄基-β-D-吡喃葡萄糖苷（4）与3,4,6-三-O-苄基-2-O-氯二甲基甲硅烷基-1-硫代-β-D-吡喃葡萄糖苷乙酯进行硅烷化反应，以35%的产率得到苄基2-O-（3,4,6-三-O-苄基-1-S-乙基-1-硫代-β-D-吡喃葡萄糖-2-O-基二甲基甲硅烷基）-3,4,6-三-O-苄基-β-D-吡喃葡萄糖苷（5）。5与N-碘代琥珀酰亚胺在硝基甲烷中反应，以45%的产率得到苄基2-O-（3,4,6-三-O-苄基-α-D-吡喃葡萄糖基）-3,4,6-三-O-苄基-β-D-吡喃葡萄糖苷（6）。苯基3,4,6-三-O-乙酰基-1-硒代-α-D-吡喃葡萄糖苷（2α）进行氯二甲基硅烷化反应并与6反应，以82%的产率得到苄基2-O-[2-O-（3,4,6-三-O-乙酰基-1-Se-苯基-1-硒代-α-D-吡喃葡萄糖-2-O-基二甲基甲硅烷基）-3,4,6-三-O-苄基-α-D-吡喃葡萄糖基]-3,4,6-三-O-苄基-β-D-吡喃葡萄糖苷（7）。7在硝基甲烷中使用N-碘代琥珀酰亚胺进行分子内糖苷化反应，以45%的产率得到苄基2-O-[2-O-（3,4,6-三-O-乙酰基-α-D-吡喃葡萄糖基）-3,4,6-三-O-苄基-α-D-吡喃葡萄糖基]-3,4,6-三-O-苄基-β-D-吡喃葡萄糖苷（8）。8脱保护定量得到曲菌素（9）。1,3,4,6-四-O-苄基-α,β-D-呋喃果糖（10）与二甲基二氯硅烷和吡啶进行氯二甲基硅烷化反应，然后与3,4,6-三-O-苄基-1-硫代-β-D-吡喃葡萄糖苷（3）反应，以85%的产率得到乙基2-O-（1,3,4,6-四-O-苄基-α,β-D-呋喃果糖氧基二甲基甲硅烷基）-3,4,6-三-O-苄基-1-硫代-β-D-吡喃葡萄糖苷（11）。1,3,4,6-四-O-苯甲酰基-α-D-呋喃果糖（12）与二甲基二氯硅烷和三乙胺进行氯二甲基硅烷化反应，然后与苯基3,4,6-三-O-乙酰基-1-硫代-α-D-吡喃葡萄糖苷（13）反应，以62%的产率得到苯基2-O-（1,3,4,6-四-O-苯甲酰基-α-D-呋喃果糖氧基二甲基甲硅烷基）-3,4,6-三-O-乙酰基-1-硫代-α-D-吡喃葡萄糖苷（14）。11和14均未发生分子内糖苷化反应。
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