(-)-gabosine I | 334917-69-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-gabosine I
• 英文别名: gabosine I；valienone；(4R,5S,6R)-4,5,6-trihydroxy-3-(hydroxymethyl)cyclohex-2-en-1-one
• CAS: 334917-69-0
• 化学式: C₇H₁₀O₅
• 分子量: 174.153
• InChiKey: WQMTVIWUDHFWNR-VQVTYTSYSA-N

物化性质

• 沸点：
  429.4±45.0 °C(Predicted)
• 密度：
  1.678±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.5
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  98
• 氢给体数：
  4
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-gabosine I 在 L-谷氨酰胺 、 磷酸吡哆醛 、 aminotransferase from bacillus circulans 作用下， 以 aq. phosphate buffer 为溶剂， 反应 3.0h， 生成 (1S,2S,3R,6R)-6-amino-4-(hydroxymethyl)cyclohex-4-ene-1,2,3-triol
  参考文献：
  名称：

  A new pre-column derivatization for valienamine and beta-valienamine using o-phthalaldehyde to determine the epimeric purity by HPLC and application of this method to monitor enzymatic catalyzed synthesis of beta-valienamine

  摘要：

  Valienamine and -valienamine are representative C7N aminocyclitols with significant glycosidase inhibition activity that have been developed as important precursors of drugs for diabetes and lysosomal storage diseases, respectively. The quantitative analysis of these chiral compounds is crucial for asymmetric in vitro biosynthetic processes for converting valienone into valienamine epimers using aminotransferase. Here, we developed an efficient and sensitive method for separation and quantitative analysis of chiral valienamine using reversed-phase high-performance liquid chromatography (HPLC) through o-phthalaldehyde (OPA) pre-column derivatization of the analytes. The epimers were derivatized by OPA in borate buffer (pH 9.0) at room temperature for 30 s, separated on an Eclipse XDB-C18 (5m, 4.6x150mm) column, eluted with 22% acetonitrile at 30 degrees C for 18min, and detected by a fluorescence detector using 445nm emission and 340nm excitation wavelengths. The average resolution of the epimers is 3.86, and the concentration linearity is in the range of 0.02-20g/ml. The method proved to be effective, sensitive, and reliable with good intra- and inter-day precision and accuracy, and successfully evaluated the enantiopreference and catalytic capability of the potential aminotransferases on an unnatural prochiral substrate, facilitating the design of an asymmetric biosynthetic route for optically pure valienamine and -valienamine.[GRAPHICS].

  DOI：

  10.1080/10286020.2017.1292257
• 作为产物：
  描述：

  葡萄糖酸内酯 在 2,6-二甲基吡啶 、 sodium tetrahydroborate 、 四丁基碘化铵 、 二甲基亚砜 、 三氟乙酸 、 三氟乙酸酐 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 66.33h， 生成 (-)-gabosine I
  参考文献：
  名称：

  从 δ-d-葡糖酸内酯快速高效地合成 Gabosine I、Streptol、7-O-Acetylstreptol、1-epi-Streptol、Gabosine K 和 Carba-α-d-葡萄糖

  摘要：

  δ-D-葡萄糖酸内酯在四步中被碳环化为 EOM 保护的环己烯酮，包括过乙氧基甲基化、膦酸阴离子加成、还原和氧化，同时伴随着 Horner-Wadsworth-Emmons 烯化。稳定的关键烯酮被有效地转化为 gabosine 1（五步，δ-D-葡萄糖酸内酯的总产率为 65%）、链霉醇（六步，总产率 54%）、7-O-乙酰-链醇（七步，42%总产率）、1-表链糖醇（六步，总产率 49%）、加波辛 K（七步，总产率 40%）和卡巴-α-D-吡喃葡萄糖（七步，总产率 47%）。目前的化学合成，从市售的 δ-D-葡萄糖酸内酯，提供了迄今为止这些分子的最高总产率。

  DOI：

  10.1055/s-0030-1260547

文献信息

• Short Syntheses of Gabosine I and Gabosine G from δ-<scp>d</scp>-Gluconolactone
  作者：Tony K. M. Shing、Hau M. Cheng

  DOI：10.1021/jo0709697

  日期：2007.8.1

  A short synthesis of gabosine I (1) from δ-d-gluconolactone (3) in four steps, involving a one-pot TPAP oxidation−K2CO3-mediated intramolecular Horner−Wadsworth−Emmons (HWE) olefination as the key step, is described. Regioselective acetylation of the primary alcohol in gabosine I (1) then furnished gabosine G (2).

  从δ-d-葡萄糖酸内酯（3）的四个步骤中短暂合成合成的Gabosine I（1），涉及一锅TPAP氧化-K 2 CO 3介导的分子内霍纳-沃兹沃思-埃蒙斯（HWE）烯化反应为关键步骤进行说明。然后在Gabosine I（1）中对伯醇进行区域选择性乙酰化，从而提供了Gabosine G（2）。
• Total Syntheses of (+)-Gabosine P, (+)-Gabosine Q, (+)-Gabosine E, (−)-Gabosine G, (−)-Gabosine I, (−)-Gabosine K, (+)-Streptol, and (−)-Uvamalol A by a Diversity-Oriented Approach Featuring Tunable Deprotection Manipulation
  作者：Po Yuan、Xiaojing Liu、Xing Yang、Yanli Zhang、Xiaochuan Chen

  DOI：10.1021/acs.joc.7b00181

  日期：2017.4.7

  A new diversity-oriented approach to C7-cyclitols, which possess a broad spectrum of biological activities, is developed. The key polyoxygenated intermediates with different O-protecting groups were accessed by an intramolecular aldol-cyclization of a diketone derived from δ-d-gluconolactone. The versatile intermediates can be easily transformed into structurally different carbasugars based on control

  开发了一种具有多样性的生物活性的，面向多样性的C7-环醇新方法。通过衍生自δ - d的二酮的分子内醛醇缩合反应，可以得到具有不同O保护基的关键多氧化中间体。-葡糖酸内酯。基于脱保护操作的控制，可以轻松地将通用中间体转变为结构上不同的碳糖。鲁棒方法的实用性由（+）-糖精P和Q的第一个合成，以及其他几个糖精和相关类似物的合成来说明。（+）-糖精E，（-）-糖精G，（-）-糖精I，（-）-糖精K，（+）-链烷醇和（-）-草胺醇A.此外，（ −）-uvamalol A通过其总合成进行分配。
• ValC, a New Type of C7-Cyclitol Kinase Involved in the Biosynthesis of the Antifungal Agent Validamycin A
  作者：Kazuyuki Minagawa、Yirong Zhang、Takuya Ito、Linquan Bai、Zixin Deng、Taifo Mahmud

  DOI：10.1002/cbic.200600528

  日期：2007.4.16

  thus suggesting a critical function of valC in validamycin biosynthesis. In vitro characterization of ValC revealed a new type of C7-cyclitol kinase, which phosphorylates valienone and validone--but not 2-epi-5-epi-valiolone, 5-epi-valiolone, or glucose--to afford their 7-phosphate derivatives. The results provide new insights into the activity of this enzyme and also confirm the existence of two

  在有效霉素A生物合成基因簇中鉴定出了基因valC，该基因编码与阿卡波糖生物合成途径的2-epi-5-epi-valiolone激酶（AcbM）同源的酶。valC的失活导致突变体缺乏产生有效霉素的能力。带有全长valC的复制质粒的互补实验恢复了有效霉素A的产生，因此表明valC在有效霉素的生物合成中具有关键作用。ValC的体外表征揭示了一种新型的C7-环糖醇激酶，可磷酸化瓦伦酮和有效酮，而不是2-epi-5-epi-valiolone，5-epi-valiolone或葡萄糖，以提供其7-磷酸酯衍生品。结果提供了对该酶活性的新见解，并证实了导致相同终产物的两种不同途径的存在：
• Carbocyclization of d-glucose: syntheses of gabosine I and streptol
  作者：Tony K.M. Shing、Y. Chen、Wai-Lung Ng

  DOI：10.1016/j.tet.2011.06.028

  日期：2011.8

  D-Glucose was differentially protected with a trans-diacetal at C-2,3, an ethoxymethyl ether at C-4, and a tert-butyldimethylsilyl ether at C-6, and then carbocyclized via a key Horner-Wadsworth-Emmons (HWE) olefination to give a versatile synthetic intermediate, enone 13, which was readily transformed into gabosine I and streptol. (C) 2011 Elsevier Ltd. All rights reserved.
• New Access to Unsaturated Keto Carba Sugars (Gabosines) Using an Intramolecular Nozaki−Kishi Reaction as the Key Step
  作者：André Lubineau、Isabelle Billault

  DOI：10.1021/jo980309p

  日期：1998.8.1