xyolide | 1446245-92-6

• 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: xyolide
• 英文别名: 4-(((5S,8S,9S,10R,E)-10-heptyl-8,9-dihydroxy-2-oxo-3,4,5,8,9,10-hexahydro-2H-oxecin-5-yl)oxy)-4-oxobutanoic acid；(+)-Xyolide；4-[[(2R,3S,4S,5E,7S)-2-heptyl-3,4-dihydroxy-10-oxo-2,3,4,7,8,9-hexahydrooxecin-7-yl]oxy]-4-oxobutanoic acid
• CAS: 1446245-92-6
• 化学式: C₂₀H₃₂O₈
• 分子量: 400.469
• InChiKey: OUOHBCJNWADUGG-KBDQXCAPSA-N

物化性质

• 沸点：
  606.8±55.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  28
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  130
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  (1R)-1-[(4R,5S)-5-ethenyl-2,2-dimethyl-1,3-dioxolan-4-yl]octyl (4S)-4-hydroxyhex-5-enoate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 盐酸 、 4-二甲氨基吡啶 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 17.5h， 生成 xyolide
  参考文献：
  名称：

  立体选择性的全合成木聚糖，一种天然的生物活性壬内酯

  摘要：

  已经完成了自然存在的生物活性壬烯内酯二甲酸酯的立体选择性全合成。该分子的酸片段是由D-甘露醇制备的，而醇片段是由（2 Z）-丁-2-烯-1,4-二醇制备的。合成过程涉及使用Yamaguchi酯化方案将这两个片段偶联，然后进行分子内闭环置换。通过采用Mitsunobu酯化反应，非对映异构醇片段也已用于该合成中。

  DOI：

  10.1002/hlca.201400291

文献信息

• A Carbohydrate-Based Approach for the Total Synthesis of Xyolide
  作者：Debendra Mohapatra、D. Reddy、Dnyaneshwar Karhale、Jhillu Yadav

  DOI：10.1055/s-0033-1339896

  日期：——

  We have achieved a total synthesis of xyolide, a bioactive nonenolide, by following a carbohydrate-based approach starting from d -(–)-ribose. The key reactions involved epoxide opening with a long-chain aliphatic Grignard reagent, Yamaguchi esterification, and a ring-closing-metathesis reaction. The longest linear sequence was nine steps and the overall yield was 30%.

  通过从 d -(-)-核糖开始，采用基于碳水化合物的方法，我们已经实现了木内酯（一种生物活性壬烯醇内酯）的全合成。关键反应包括环氧化物与长链脂肪族格氏试剂的开环、山口酯化和闭环复分解反应。最长的线性序列为 9 步，总产率为 30%。
• Total Synthesis of the Nonenolide Xyolide Using a Regioselective Nucleophilic Epoxide Opening Approach
  作者：A. Narsaiah、Sachin Wadavrao、Ramesh Ghogare

  DOI：10.1055/s-0034-1380780

  日期：——

  Abstract The total synthesis of the nonenolide xyolide is described as a convergent synthesis in 16 steps from the commercially available starting material butane-1,4-diol. The key reactions involved are: Sharpless­ asymmetric epoxidation, Pinnick oxidation, acid-mediated nucleophilic regioselective epoxide ring opening, Steglich esterification, and ring-closing metathesis. The total synthesis of the nonenolide

  摘要 壬烯基内酯的总合成被描述为由市售原料丁烯1，，4-二醇分16步进行的收敛合成。涉及的关键反应是：无尖锐的不对称环氧化，Pinnick氧化，酸介导的亲核区域选择性环氧化物的开环，Steglich酯化和闭环易位。 壬烯基内酯的总合成被描述为由市售原料丁烯1，，4-二醇分16步进行的收敛合成。涉及的关键反应是：无尖锐的不对称环氧化，Pinnick氧化，酸介导的亲核区域选择性环氧化物的开环，Steglich酯化和闭环易位。
• Stereoselective total synthesis of xyolide
  作者：B.V. Subba Reddy、P. Sivaramakrishna Reddy、B. Phaneendra Reddy、J.S. Yadav、Ahamad Al Khazim Al Ghamdi

  DOI：10.1016/j.tetlet.2013.08.038

  日期：2013.10

  A stereoselective total synthesis of xyolide is described employing MacMillan α-hydroxylation, Steglich esterification, and ring closing metathesis as key steps. The use of organocatalytic MacMillan α-hydroxylation to construct two of the chiral centers of the xyolide makes this approach attractive.

  描述了使用MacMillanα-羟基化，Steglic酯化和闭环复分解为关键步骤的二甲苯甲酸酯的立体选择性全合成。使用有机催化MacMillanα-羟基化来构建二氧内酯的两个手性中心使该方法具有吸引力。
• Asymmetric synthesis of naturally occurring nonenolide xyolide through cross metathesis and macrolactonization reaction
  作者：Rohan Kalyan Rej、Anuvab Jana、Samik Nanda

  DOI：10.1016/j.tet.2014.02.072

  日期：2014.4

  Asymmetric total synthesis of xyolide, a small ring macrolide is presented in this article. The synthesis is achieved through an 'E' selective cross metathesis (CM) reaction between two appropriate fragments followed by lactonization by Shiina method. One of the fragments containing 7S,8S,9R stereocenters of xyolide is accessed from n-nonanal by adopting an organocatalytic asymmetric alpha-aminooxylation, Z-selective Ando olefination, and substrate directed dihydroxylation reaction. The other fragments containing 4S stereocenter was prepared by ME-DKR (metal enzyme combined dynamic kinetic resolution) method. (C) 2014 Elsevier Ltd. All rights reserved.
• A Stereoselective Total Synthesis of Xyolide, a Natural Bioactive Nonenolide
  作者：Lingaiah Maram、Biswanath Das

  DOI：10.1002/hlca.201400291

  日期：2015.5

  A stereoselective total synthesis of xyolide, a naturally occurring bioactive nonenolide, has been accomplished. The acid fragment of the molecule has been prepared from D‐mannitol and the alcohol fragment from (2Z)‐but‐2‐ene‐1,4‐diol. The synthesis involves the coupling of these two fragments using the Yamaguchi esterification protocol, followed by intramolecular ring‐closing methathesis. The diastereoisomeric

  已经完成了自然存在的生物活性壬烯内酯二甲酸酯的立体选择性全合成。该分子的酸片段是由D-甘露醇制备的，而醇片段是由（2 Z）-丁-2-烯-1,4-二醇制备的。合成过程涉及使用Yamaguchi酯化方案将这两个片段偶联，然后进行分子内闭环置换。通过采用Mitsunobu酯化反应，非对映异构醇片段也已用于该合成中。