(-)-1-epi-valiolamine | 141042-85-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-1-epi-valiolamine
• 英文别名: (-)-Epivaliolamine；(1S,2S,3R,4S,5R)-5-amino-1-(hydroxymethyl)cyclohexane-1,2,3,4-tetrol
• CAS: 141042-85-5
• 化学式: C₇H₁₅NO₅
• 分子量: 193.2
• InChiKey: VDLOJRUTNRJDJO-UOYQFSTFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.3
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  127
• 氢给体数：
  6
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (-)-1-epi-valiolamine 在 4-二甲氨基吡啶 作用下， 以 吡啶 为溶剂， 以80%的产率得到1L-(1,2,4/3,5)-5-acetamido-1-C-(acetoxymethyl)-2,3,4-tri-O-acetyl-1,2,3,4-cyclohexanetetraol
  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
• 作为产物：
  描述：

  1L-(1,2,4/3,5)-1-C-(acetoxymethyl)-2,3,4,5-tetra-O-acetyl-1,2,3,4,5-cyclohexanepentol 在 Raney nickel T-4 吡啶 、 盐酸 、 4-二甲氨基吡啶 、 sodium azide 、 氢气 、 sodium methylate 、 对甲苯磺酸 作用下， 以 甲醇 、 乙二醇甲醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 75.5h， 生成 (-)-1-epi-valiolamine
  参考文献：
  名称：

  从（-）-vibo-槲皮醇方便地合成（+）-缬胺和（-）-1-表-缬胺。

  摘要：

  描述了由（-）-维-槲皮醇，1-脱氧-L-肌醇，通过肌醇的生物转化而容易地合成（+）-缬胺和（-）-1-表-缬胺的便捷实用方法。 。

  DOI：

  10.1039/b314795a

文献信息

• Total Syntheses of (+)-Valiolamine and (-)-1-<i>epi</i>-Valiolamine from Naturally Abundant (-)-Shikimic Acid
  作者：Na Quan、Liang-Deng Nie、Rui-Heng Zhu、Xiao-Xin Shi、Wei Ding、Xia Lu

  DOI：10.1002/ejoc.201300804

  日期：2013.10

  Total syntheses of (+)-valiolamine (1) and (–)-1-epi-valiolamine (2) from the naturally abundant (–)-shikimic acid are described. Ethyl 3-epi-5-O-methylsulfonyl-shikimate (3), as the key common intermediate, was first synthesized in five steps in 74 % overall yield, and then converted into the targets 1 and 2 in seven steps in 48 and 41 % overall yield, respectively.

  描述了从天然丰富的 (-)-莽草酸合成 (+)-valiolamine (1) 和 (-)-1-epi-valiolamine (2)。3-epi-5-O-甲基磺酰基-莽草酸乙酯(3)作为关键的常用中间体，首先分五步合成，总产率为74%，然后在48和41分七步转化为目标1和2 % 总产率，分别。
• Synthesis of valiolamine and its N-substituted derivatives AO-128, validoxylamine G, and validamycin G via branched-chain inosose derivatives
  作者：Hiroshi Fukase、Satoshi Horii

  DOI：10.1021/jo00039a026

  日期：1992.6

  Novel synthetic routes to valiolamine (1a) and N-substituted valiolamine derivatives via branched-chain inosose derivatives are described. (1S)-(1(OH),2,4/1,3)-2,3,4-Tri-O-benzyl-1-C-[(benzyloxy)methyl]-5-oxo-1,2,3,4-cyclohexanetetrol (3), a branched-chain inosose derivative prepared from D-glucose, 2 has been converted into 1a via the ketoxime 7 followed by hydrogenation. N-Substituted valiolamine derivatives having strong alpha-D-glucosidase inhibitory activity have been synthesized by the direct reductive amination of the branched-chain inosose derivative 3 with an appropriate amino compound to construct the N-substituent moiety, followed by removal of the O-benzyl protecting group. The stereoselective preparation of two representative derivatives, N-[2-hydroxy-1-(hydroxymethyl)ethyl]valiolamine (2a, AO-128)3 and N-[1R,2R)-2-hydroxyclohexyl]valiolamine (2b)3 is described. Application of branched-chain inosose derivatives 3 and 23 to the total synthesis of natural N-substituted valiolamine derivatives validoxylamine G (5a) and validamycin G (6a) is also described.
• 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：——