(1S,2S,3S,4R,5R)-1,2-di-O-acetyl-3-O-benzyl-1-benzyloxymethyl-1,2,3,4,5-cyclohexanepentaol | 171252-88-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,2S,3S,4R,5R)-1,2-di-O-acetyl-3-O-benzyl-1-benzyloxymethyl-1,2,3,4,5-cyclohexanepentaol
• 英文别名: (1R,2R,3R,4S,5S)-4,5-di-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)cyclohexane-1,2,3,4,5-pentol；[(1S,2S,4R,5R,6R)-2-acetyloxy-4,5-dihydroxy-6-phenylmethoxy-2-(phenylmethoxymethyl)cyclohexyl] acetate
• CAS: 171252-88-3
• 化学式: C₂₅H₃₀O₈
• 分子量: 458.508
• InChiKey: FRFOQKGTHDEXLN-LFCBLZOASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  33
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  112
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (1S,2S,3S,4R,5R)-1,2-di-O-acetyl-3-O-benzyl-1-benzyloxymethyl-1,2,3,4,5-cyclohexanepentaol 在 palladium dihydroxide 吡啶 、 sodium azide 、 苯并-15-冠醚-5 、 氢气 、 potassium carbonate 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 井冈霉醇胺
  参考文献：
  名称：

  Shing, Tony K. M.; Wan, Leong H., Angewandte Chemie, 1995, vol. 107, # 15, p. 1742 - 1744

  摘要：

  DOI：
• 作为产物：
  描述：

  (1R,2R,3S,4S,5S)-3-O-benzyl-5-((benzyloxy)methyl)-1,2-O-cyclohexylidenecyclohexane-1,2,3,4,5-pentol 在 4-二甲氨基吡啶 、 水 、 三氟乙酸 作用下， 以 二氯甲烷 、 三乙胺 为溶剂， 反应 27.0h， 生成 (1S,2S,3S,4R,5R)-1,2-di-O-acetyl-3-O-benzyl-1-benzyloxymethyl-1,2,3,4,5-cyclohexanepentaol
  参考文献：
  名称：

  Facile Syntheses of Valiolamine and Its Diastereomers from (−)-Quinic Acid.¹ Nucleophilic Substitution Reactions of 5-(Hydroxymethyl)cyclohexane-1,2,3,4,5-pentol

  摘要：

  Valiolamine (1), 1-epi-valiolamine (2), 2-epi-valiolamine (3), (1R,2R)-valiolamine (4), and 2-amino regioisomer 17 have been prepared from (-)-quinic acid (6) in 14 (8.4% overall yield), 13 (9.0%), 15 (4.3%), 17 steps (2.5%), and 12 steps (13%), respectively. Charged nucleophilic ring-openings of cyclic sulfate (1R,2S,3S,4S,5S)-4,5-di-O-acetyl-3-O-benzyl-5-(benzyloxymethyl)-1,2-O,O-sulfonyl-cyclohexane-1,2,3,4,5-pentol (11) occurred regioselectively at C-2, whereas the corresponding ring-openings of its (1S,2R)-diastereomer 34 proceeded preponderantly at C-1. (1R,2S,3R,4S,5S)-2,4,5-Tri-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)-1-O-(trifluoromethanesulfonyl) cyclohexane-1,2,3,4,5-pentol (24) underwent novel internal displacement spontaneously to form (1S,2S,3R,4S,5S)-1,2,4-tri-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)cyclohexane-1,2,3,4,5-pentol (25), whereas its 2-epimer was inert under the same conditions. Ruthenium-catalyzed dihydroxylation of alkene, (3R,4S,5S)-4,5-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)-1-cyclohexene-3,4,5-triol (31), gave the desired beta-1,2-diol 32 in higher yield and stereoselectivity than the osmium tetraoxide protocol. The regioselectivity of charged nucleophilic ring-openings of cyclic sulfates 11, 34, and 38 is discussed.

  DOI：

  10.1021/jo9607828

文献信息

• Shing, Tony K. M.; Tam, Eric K. W.; Tai, Vincent W.-F., Chemistry - A European Journal, 1996, vol. 2, # 1, p. 50 - 57
  作者：Shing, Tony K. M.、Tam, Eric K. W.、Tai, Vincent W.-F.、Chung, Ivan H. F.、Jiang, Qin

  DOI：——

  日期：——
• Shing, Tony K. M.; Wan, Leong H., Angewandte Chemie, 1995, vol. 107, # 15, p. 1742 - 1744
  作者：Shing, Tony K. M.、Wan, Leong H.

  DOI：——

  日期：——
• Facile Syntheses of Valiolamine and Its Diastereomers from (−)-Quinic Acid.¹ Nucleophilic Substitution Reactions of 5-(Hydroxymethyl)cyclohexane-1,2,3,4,5-pentol
  作者：Tony K. M. Shing、Leong H. Wan

  DOI：10.1021/jo9607828

  日期：1996.1.1

  Valiolamine (1), 1-epi-valiolamine (2), 2-epi-valiolamine (3), (1R,2R)-valiolamine (4), and 2-amino regioisomer 17 have been prepared from (-)-quinic acid (6) in 14 (8.4% overall yield), 13 (9.0%), 15 (4.3%), 17 steps (2.5%), and 12 steps (13%), respectively. Charged nucleophilic ring-openings of cyclic sulfate (1R,2S,3S,4S,5S)-4,5-di-O-acetyl-3-O-benzyl-5-(benzyloxymethyl)-1,2-O,O-sulfonyl-cyclohexane-1,2,3,4,5-pentol (11) occurred regioselectively at C-2, whereas the corresponding ring-openings of its (1S,2R)-diastereomer 34 proceeded preponderantly at C-1. (1R,2S,3R,4S,5S)-2,4,5-Tri-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)-1-O-(trifluoromethanesulfonyl) cyclohexane-1,2,3,4,5-pentol (24) underwent novel internal displacement spontaneously to form (1S,2S,3R,4S,5S)-1,2,4-tri-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)cyclohexane-1,2,3,4,5-pentol (25), whereas its 2-epimer was inert under the same conditions. Ruthenium-catalyzed dihydroxylation of alkene, (3R,4S,5S)-4,5-O-acetyl-3-O-benzyl-5-((benzyloxy)methyl)-1-cyclohexene-3,4,5-triol (31), gave the desired beta-1,2-diol 32 in higher yield and stereoselectivity than the osmium tetraoxide protocol. The regioselectivity of charged nucleophilic ring-openings of cyclic sulfates 11, 34, and 38 is discussed.