1,3,4,6-tetra-O-benzoyl-α-D-fructofuranose | 80763-56-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3,4,6-tetra-O-benzoyl-α-D-fructofuranose
• 英文别名: 1,3,4,6-Tetra-O-benzoyl-alpha-D-fructofuranose；[(2R,3R,4S,5S)-3,4-dibenzoyloxy-5-(benzoyloxymethyl)-5-hydroxyoxolan-2-yl]methyl benzoate
• CAS: 80763-56-0
• 化学式: C₃₄H₂₈O₁₀
• 分子量: 596.59
• InChiKey: ZYJUUZKDMZKDIS-NPDJUGFLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  44
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  135
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1,3,4,6-tetra-O-benzoyl-α-D-fructofuranose 在 2,4,6-三甲基吡啶 、 氢溴酸 、 triphenylmethyl perchlorate 、 乙酸酐 作用下， 以 二氯甲烷 、 氯仿 、 水 、 溶剂黄146 、 乙腈 为溶剂， 反应 1.5h， 生成 1,2:3,4-di-O-isopropylidene-6-O-(1,3,4,6-tetra-O-benzoyl-α-D-fructofuranosyl)-α-D-galactopyranose
  参考文献：
  名称：

  Glycosylation by d-fructofuranose thio-orthoesters

  摘要：

  DOI：

  10.1016/s0008-6215(00)81909-6
• 作为产物：
  描述：

  α-D-fructofuranose 、 苯甲酰氯 在 吡啶 作用下， 反应 0.25h， 以69%的产率得到1,3,4,6-tetra-O-benzoyl-α-D-fructofuranose
  参考文献：
  名称：

  Glycosylation by d-fructofuranose thio-orthoesters

  摘要：

  DOI：

  10.1016/s0008-6215(00)81909-6

文献信息

• Stereocontrolled synthesis of α-d-allulofuranosides using α-selective d-fructofuranosidation reaction
  作者：Akihiro Iyoshi、Yui Makura、Masakazu Tanaka、Atsushi Ueda

  DOI：10.1016/j.carres.2024.109044

  日期：2024.2

  Stereocontrolled synthesis of rare sugar derivatives, namely α-d-allulofuranosides, was achieved using d-fructose, one of the most abundant carbohydrates in nature. The following are the key steps of the α-d-allulofuranosides’ synthesis. (1) An α-selective glycosidation reaction of 1,3,4,6-tetra-O-benzoylated d-fructofuranosyl donor to obtain α-d-fructofuranosides with 98 %–75 % isolated yields. (2)

  使用自然界中最丰富的碳水化合物之一的d-果糖，实现了稀有糖衍生物（即 α- d-呋喃糖苷）的立体控制合成。以下是α- d-呋喃糖苷合成的关键步骤。 (1) 1,3,4,6-四-O-苯甲酰化d-呋喃果糖基供体进行α-选择性糖苷化反应，得到α- d-呋喃果糖苷，分离收率98%–75%。 (2) α- d-呋喃果糖苷四醇的区域选择性 1,4,6-三-O-新戊酰化反应，且 C3-羟基保持完整。 (3)C3-羟基的氧化，随后C3-羰基的立体选择性还原。伯醇、仲醇和糖可以作为糖基受体和苷元进行后续的新戊酰化和立体反转反应，得到α- d-阿洛呋喃糖苷。
• Lichtenthaler, Frieder W.; Klotz, Juergen; Flath, Franz-Josef, Liebigs Annalen, 1995, # 12, p. 2069 - 2080
  作者：Lichtenthaler, Frieder W.、Klotz, Juergen、Flath, Franz-Josef

  DOI：——

  日期：——
• Chretien, Francoise; Cesare, Pierre Di; Gross, Bernard, Journal of the Chemical Society. Perkin transactions I, 1988, p. 3297 - 3300
  作者：Chretien, Francoise、Cesare, Pierre Di、Gross, Bernard

  DOI：——

  日期：——
• Synthesis of Kojitriose using Silicon-Tethered Glycosidation.
  作者：Mikael Bols、Christian Orrenius、Niklas Öhrner、C. Rikard Unelius、Karl Hult、Torbjörn Norin、Muhammed Nour Homsi、Frank K. H. Kuske、Monika Haugg、Nathalie Trabesinger-Rüf、Elmar G. Weinhold

  DOI：10.3891/acta.chem.scand.50-0931

  日期：——

  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-yldimethylsilyl)-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-yldimethylsilyl) -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 dimethyldichlorosilane 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.