valienamine | 74645-52-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: valienamine
• 英文别名: valienamine pentaacetate；[(3R,4R,5R,6S)-3-acetamido-4,5,6-triacetyloxycyclohexen-1-yl]methyl acetate
• CAS: 74645-52-6
• 化学式: C₁₇H₂₃NO₉
• 分子量: 385.371
• InChiKey: BGWUDGFQBITPFE-YYIAUSFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.21
• 重原子数：
  27.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  134.3
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  valienamine 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.5h， 以96%的产率得到N-((1S,4R,5S,6S)-4,5,6-trihydroxy-3-(hydroxymethyl)cyclohex-2-en-1-yl)acetamide
  参考文献：
  名称：

  Synthesis of some valienamine epoxides: on the structure of the alpha-amylase inhibitor NS-504

  摘要：

  DOI：

  10.1016/0008-6215(88)84151-x
• 作为产物：
  描述：

  (1S)-(1,3,6/2)-1,2,3-triacetoxy-4-acetoxymethyl-6-azidocyclohex-4-ene 在 吡啶 、 sodium tetrahydroborate 作用下， 以 异丙醇 为溶剂， 反应 3.5h， 生成 valienamine
  参考文献：
  名称：

  Validamycins 的合成研究。四、DL-缬草胺及相关支链不饱和氨基环醇的合成

  摘要：

  缬草胺的外消旋物及其相关的支链不饱和氨基环醇已首次合成。开发了两条合成缬草胺的路线，其中之一是立体选择性和高效的。关键的转化是烯丙基氯上叠氮化物离子的立体特异性 SN2' 攻击（表面），通过共轭二烯的区域选择性环氧化，然后用盐酸处理来制备。描述了一些信息，这些信息由新的支链不饱和氨基环醇和环醇的 13C NMR 光谱提供。

  DOI：

  10.1246/bcsj.56.1161

文献信息

• Total Synthesis of (±)- and (+)-Valienamine via a Strategy Derived from New Palladium-Catalyzed Reactions
  作者：Barry M. Trost、Louis S. Chupak、Thomas Lübbers

  DOI：10.1021/ja973081g

  日期：1998.3.1

  such an inhibitor itself as well as a critical unit of pseudooligosaccharides that function this way, evolved from two newly developed palladium-catalyzed reactions. The applicability of a palladium(0)-catalyzed net regioselective cis-hydroxyamination derives from the reaction of vinyl epoxides with isocyanates. The utilization of a cocatalyst in this reaction is required in this case and may prove generally

  以缬草胺为代表的糖苷酶抑制剂的新策略是从两种新开发的钯催化反应演化而来的，缬草胺本身就是这种抑制剂，也是以这种方式发挥作用的假寡糖的关键单元。钯 (0) 催化的净区域选择性顺式羟基胺化的适用性源自乙烯基环氧化物与异氰酸酯的反应。在这种情况下需要在该反应中使用助催化剂，并且通常证明是有用的。二齿亚磷酸酯被证明是最有效的配体。所需的底物可通过 Diels-Alder 协议获得，并且只需要 7 个步骤即可获得 (±)-缬草胺。无法不对称地进行 Diels-Alder 反应导致对映异构纯形式的关键环氧化物中间体的不同不对称合成，其源自不对称钯催化反应。使用内消旋烯二羧酸酯的去对称化，不对称的净等价...
• SYNTHESIS OF PENTA-<i>N</i>,<i>O</i>-ACETYL-DL-VALIENAMINE AND ITS RELATED BRANCHED-CHAIN UNSATURATED AMINOCYCLITOLS AND CYCLITOLS
  作者：Seiichiro Ogawa、Tatsushi Toyokuni、Tetsuo Suami

  DOI：10.1246/cl.1980.713

  日期：1980.6.5

  Penta-N,O-acetyl-Dl-valienamine, and its related branched-chain unsaturated aminocyclitols and cyclitols were synthesized from the dibromides derived from tri-O-acetyl-Dl-(1,3/2)-4-methylene-5-cyclohexene-1,2,3-triol.

  从三-O-乙酰基-Dl-(1,3/2)-4-亚甲基-5-环己烯-1,2,3-三醇衍生的二溴化物中合成了五-N,O-乙酰基-Dl-缬烯胺及其相关的支链不饱和氨基环醇和环醇。
• Diversification of Simple Arenes into Complex (Amino)cyclitols
  作者：Elisa Angelini、Matteo Martinelli、Eugenio Roà、Chad N. Ungarean、Christophe Salome、Quentin Lefebvre、Colin Bournez、Thomas C. Fessard、David Sarlah

  DOI：10.1002/chem.202303262

  日期：2024.1.26

  This work presents a systematic approach for accessing complex natural and non-natural (amino)cyclitols from simple arenes. A key feature includes the application of a dearomative functionalization with arenophiles and subsequent diversification, generating a widespread library of compounds spanning far into underexplored chemical space.

  这项工作提出了一种从简单的芳烃中获取复杂的天然和非天然（氨基）环醇的系统方法。一个关键特征包括应用亲仁体脱芳香功能化和随后的多样化，生成广泛的化合物库，跨越远至尚未探索的化学空间。
• Synthetic studies on the validamycins. 5. Synthesis of DL-hydroxyvalidamine and DL-valienamine
  作者：Seiichiro Ogawa、Noritaka Chida、Tetsuo Suami

  DOI：10.1021/jo00156a012

  日期：1983.4
• Vinylogy in Orthoester Hydrolysis: Total Syntheses of Cyclophellitol, Valienamine, Gabosine K, Valienone, Gabosine G, 1-<i>epi</i>-Streptol, Streptol, and Uvamalol A
  作者：Soumik Mondal、Annamalai Prathap、Kana M. Sureshan

  DOI：10.1021/jo401272j

  日期：2013.8.2

  C7-cyclitols represent an important category of natural products possessing a broad spectrum of biological activities. As each member of these compounds is structurally unique, the usual practice is to synthesize them individually from appropriate polyhydroxylated chiral pools. We have observed an unusual vinylogy in acid mediated hydrolysis of enol ethers of myo-inositol 1,3,5-orthoesters giving a synthetically versatile polyhydroxylated cyclohexenal intermediate. We have exploited this unprecedented reaction for developing a general strategy for the rapid and efficient syntheses of several structurally diverse natural products of C7-cyclitol family. We have made an appropriately protected advanced intermediate 25 in five steps from the cheap and commercially available myo-inositol, and this common intermediate has been used to synthesize eight natural products in racemic form. We could synthesize (+/-)-cyclophellitol in seven steps, (+/-)-valienamine in five steps, (+/-)-gabosine I in five steps, (+/-)-gabosine G in six steps, (+/-)-gabosine K in three steps, (+/-)-streptol in six steps, (+/-)-1-epi-streptol in two steps, and (+/-)-uvamalol A in five steps from this intermediate.