(3R,4S)(-) eldanolide | 85505-80-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3R,4S)(-) eldanolide
• 英文别名: (4R,5S)-eldanolide；(4R,5S)-4-methyl-5-(3-methylbut-2-enyl)oxolan-2-one
• CAS: 85505-80-2
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: ARNPQYFYGKMXGD-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3R,4S)(-) eldanolide 在 MoO5*pyridine*HMPA 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 以71%的产率得到(3R,4R,5S)-3-hydroxy-4-methyl-5-(3-methylbut-2-enyl)oxolan-2-one
  参考文献：
  名称：

  Stereoselective synthesis of C-9 to C-14 segment, a key intermediate for the total synthesis of trienomycin and micotrienins.

  摘要：

  The C-9 to C-14 segment, a key intermediate for the total synthesis of Trienomycin and Micotrienins has been synthesized, involving Sharpless asymmetric epoxidation intramolecular radical cyclisation and MoOPH hydroxylation as key steps.

  DOI：

  10.1016/s0040-4039(00)60494-x
• 作为产物：
  描述：

  (3R,4R)(-) tosyloxymethyl-4 methyl-3 butanolide-4 在 potassium carbonate 作用下， 生成 (3R,4S)(-) eldanolide
  参考文献：
  名称：

  L'eldanolide，信息素DES glandes alaires德拉pyrale德拉CANNEà苏克雷，eldana saccharina（WLK）：结构等SYNTHESE德SES德塞夫勒énantiomères

  摘要：

  描述了雄性非洲甘蔗Bor的翅腺信息素-艾考多奈的分离和结构测定，该药为埃尔达纳糖精（Wlk。）。通过将天然信息素与两种合成对映异构体的CD光谱进行比较，将绝对构型确定为（3S，4R）。

  DOI：

  10.1016/s0040-4020(01)91504-2

文献信息

• Efficient transformation of ()-2-butene-1,4-diols to α,β-butenolides: A simple synthesis of (±)-eldanolide
  作者：T.K. Chakraborty、S. Chandrasekaran

  DOI：10.1016/s0040-4039(01)81318-6

  日期：1984.1

  ()-2-Butene-1,4-diols are efficiently converted to the corresponding α,β-butenolides using silver carbonate/celite and this methodology has been applied to the synthesis of (±)-eldanolide, the wing gland pheromone of the male African sugar cane borer, (wlk)

  使用碳酸银/硅藻土将（）-2-丁烯-1,4-二醇有效地转化为相应的α，β-丁烯化物，并且该方法已应用于合成（±）-艾丹醇化物（该物质的翼腺信息素）。非洲雄性甘蔗蛀虫，（大头）
• CHIRALITY TRANSFER DURING CYCLOBUTYL–CYCLOPROPYLMETHYL–HOMOALLYL CATION REARRANGEMENT AND SYNTHESIS OF (−)-ELDANOLIDE
  作者：Yasushi Yokoyama、Masatoshi Yunokihara

  DOI：10.1246/cl.1983.1245

  日期：1983.8.5

  The (3R)-2,2-dimethyl-3-(2-methoxycarbonyl)ethylcyclobutyl cation rearranged to give (1S,2S)-1-(1-methoxy-1-methyl)ethyl-2-(2-methoxycarbonyl)ethylcyclopropane. The latter was transformed into (4R)-4-(3-methylbut-2-enyl)-4-butyrolactone with a high degree of chirality transfer. The γ-lactone was converted into (−)-eldanolide, an antipode of the wing gland pheromone of an African sugar-cane borer.

  (3R)-2,2-二甲基-3-(2-甲氧羰基)乙基环丁基阳离子重新排列后得到 (1S,2S)-1-(1-甲氧基-1-甲基)乙基-2-(2-甲氧羰基)乙基环丙烷。后者转化为(4R)-4-(3-甲基丁-2-烯基)-4-丁内酯，手性转移程度很高。γ-内酯被转化成(-)-eldanolide，这是一种非洲甘蔗螟虫翅腺信息素的反式。
• β-Substituted ketene thioacetals as β-lithioacrylate equivalents. The synthesis of (±)-eldanolide
  作者：Edward Dziadulewicz、Timothy Gallagher

  DOI：10.1016/s0040-4039(00)88955-8

  日期：1985.1

  Lithiation of 1,1-bis(phenylthio)-3-phenylthio-1-propene 3 and reaction with a range of electrophiles gave exclusively the γ-substituted product 4. This reagent has been used in a short synthesis of the pheromone, (±)-eldanolide.

  1,1-双（苯硫基）-3-苯硫基-1-丙烯3的锂化和与一系列亲电试剂的反应仅产生γ-取代的产物4。该试剂已用于信息素（±）-艾加醇化物的短合成中。
• β-Lithioacrylate Equivalents for the Synthesis of (±)-Eldanolide
  作者：Nabin C. Barua、Richard R. Schmidt

  DOI：10.1055/s-1986-31818

  日期：——

  Direct lithiation of ß-phenylthioacrylic acid and of methyl propiolate affords useful ß-lithioacrylate and ß-lithiopropionate equivalents. This is demonstrated in this paper in a convenient synthesis of (±)-eldanolide (±)-1 and in the transformation of butenolide (±)-7 into butyrolactone (±)-9, respectively.

  ß-苯硫基丙烯酸和丙酸甲酯的直接锂化反应可生成有用的ß-锂代丙烯酸酯和ß-锂代丙酸酯。本文分别以方便合成的（±）-埃达诺内酯（±）-1和丁烯内酯（±）-7转化为丁内酯（±）-9为例进行了说明。
• Regio- and Enantioselective Prenyl Anion Transfer: Application to the Total Synthesis of (−)-Rosiridol
  作者：Bor-Cherng Hong、Jang-Hsing Hong、Yann-Chien Tsai

  DOI：10.1002/(sici)1521-3773(19980302)37:4<468::aid-anie468>3.0.co;2-z

  日期：1998.3.2

  At elevated temperature (refluxing THF) prenyl anion adds regio- and enantioselectively to aldehyde 1 when a chiral, borneol-derived ligand is present. This reaction is the key stepin the first total synthesis of the monoterpene (-)-rosiridol (retrosynthesis is shown on the right). In addition, the absolute configuration of this natural product has been assigned conclusively. M=Zn, R=tBuMe2 Si.

  当存在手性，冰片来源的配体时，异戊二烯阴离子在升高的温度（回流的THF）下会向醛1的区域和对映体选择性地添加。该反应是单萜（-）-罗西多醇的第一个全合成中的关键步骤（右图显示了再合成）。另外，已经确定地分配了该天然产物的绝对构型。M ＝ Zn，R ＝ tBuMe 2 Si。